Colored photosensitive resin composition, color filter manufactured using the same, and solid-state imaging device or display device including the same

Abstract

To provide a colored photosensitive resin composition having an advantage of securing viscosity stability with time while improving straightness and surface roughness of a pattern.SOLUTION: The present invention relates to a colored photosensitive resin composition comprising (A) a pigment dispersion, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, a color filter manufactured using the same, and a solid-state imaging device or a display device comprising the color filter.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a colored photosensitive resin composition, a color filter or a solid-state imaging device produced using the same, and a device including the same. [Background technology]

[0002] Color filters are widely used in solid-state imaging devices, liquid crystal display devices, and the like, and their range of applications is rapidly expanding.

[0003] In particular, solid-state image sensors are elements made using integrated circuit technology that convert optical images into electrical signals. Recently, solid-state image sensors have been used as an IC instead of image pickup tubes, and they have the advantages of being small, lightweight, low power consumption, and long life, and are used because they can take pictures in dark places compared to image pickup tubes.

[0004] In recent years, color filters used in solid-state imaging devices such as CCDs and CMOS devices have become increasingly pixelated, leading to increasingly finer pixels. This has led to a demand for thinner film thicknesses while maintaining spectral characteristics. To meet these requirements, the pigment concentration must be increased when forming color filters using colored photosensitive resin compositions. However, in the case of blue photosensitive resin compositions, the blue and violet pigment dispersion compositions have a large average particle size of 60 nm or more, which results in a high pigment content and reduced linearity of the pattern. This also leads to a rough pattern surface, resulting in reduced light transmittance when light transmitted through a lens is incident on a photodiode from the color filter. Reducing the pigment volume average particle size to 15 nm or less improves the linearity of the pattern and reduces surface roughness, but it also reduces the dispersion stability of the pigment dispersion, resulting in reduced viscosity stability and rapid viscosity changes over time. Therefore, in the present invention, a pigment dispersion having a volume average particle size in the range of 15 to 60 nm is prepared using blue and violet pigments, and a colored photosensitive resin composition is prepared using the pigment dispersion, thereby improving the linearity of patterns, improving surface roughness, and ensuring viscosity stability.

[0005] Korean Patent Publication No. 10-2021-0063526 also describes a pigment dispersion and a colored photosensitive resin composition containing the same. The pigment dispersion includes a co-dispersion of an organic black pigment and an organic red pigment, and the average particle size of the pigment particles in the co-dispersion is less than 100 nm. However, the document only describes examples of average particle sizes of pigment particles exceeding 70 nm. When this is actually applied to a photosensitive composition for forming a color filter, the large volume average particle size reduces the linearity of the pattern during pattern formation, and poor surface roughness of the pattern leads to reduced light transmittance when light passes through the color filter in a solid-state imaging device. Furthermore, significantly reducing the volume average particle size of the pigment to less than 15 nm in an attempt to overcome this problem reduces viscosity stability. Therefore, the present invention is presented to solve the above problems. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Korean Patent Publication No. 10-2021-0063526 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention is to provide a colored photosensitive resin composition which solves the problems of pattern straightness and poor surface roughness that are encountered when using conventional colored photosensitive resin compositions, and which has excellent viscosity stability over time.

[0008] Another object of the present invention is to provide a color filter produced using the colored photosensitive resin composition, and a solid-state imaging device or a display device including the color filter. [Means for solving the problem]

[0009] The colored photosensitive resin composition of the present invention comprises (A) a pigment dispersion, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent; The (A) pigment dispersion liquid provides a colored photosensitive resin composition containing a pigment having a volume average particle size of 15 nm to 60 nm.

[0010] The present invention also provides a color filter produced using the colored photosensitive resin composition.

[0011] Furthermore, the present invention provides a solid-state imaging device or a display device including the color filter. [Effects of the Invention]

[0012] The present invention provides a colored photosensitive resin composition that contains a pigment dispersion containing a pigment having a volume average particle size of 15 nm to 60 nm, thereby allowing fine pigment to penetrate into every crosslinked space in the composition, thereby improving the surface roughness of the pattern.

[0013] Furthermore, when a pattern is formed using the colored photosensitive resin composition of the present invention, it is possible to form a pattern with excellent linearity.

[0014] Furthermore, the present invention provides an effect that the colored photosensitive resin composition of the present invention can be applied to a highly sensitive display device that includes a color filter produced from the colored photosensitive resin composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention relates to a colored photosensitive resin composition, a color filter produced using the same, and a solid-state imaging device and a display device each including the color filter.

[0016] The present invention solves the problems of pattern straightness and poor surface roughness by including a pigment dispersion containing a pigment having a volume average particle size of 15 nm to 60 nm in the composition of a colored photosensitive resin composition, has excellent viscosity stability over time, and can be applied to highly sensitive devices.

[0017] The present invention will be described in detail below. <Colored photosensitive resin composition> (A) Pigment dispersion The pigment dispersion (A) contains a pigment having a volume-average particle size of 15 nm to 60 nm. When a pigment within this volume-average particle size range is included, it has a desirable size that allows the pigment to be trapped between the photopolymerizable compound and the soluble alkali resin during crosslinking. Therefore, when the photopolymerizable compound and the colored photosensitive resin composition are cured by exposure, fine pigment particles penetrate into the crosslinked spaces of the composition, thereby improving the surface roughness of the pattern during pattern formation. If the volume-average particle size of the pigment dispersion exceeds 60 nm, the penetration of the pigment between the cured photopolymerizable compound and the colored photosensitive resin composition becomes relatively difficult, resulting in a decrease in the surface roughness improvement effect compared to particle sizes within the effective range and poor pattern linearity. If the volume-average particle size of the pigment dispersion is less than 15 nm, the surface area of ​​the pigment particles increases, leading to aggregation, which causes problems with viscosity stability.

[0018] The pigment dispersion may include a blue pigment or a violet pigment.

[0019] The blue pigment that can be used in the present invention may be one or more selected from the group consisting of blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 60, and among these, CI Pigment Blue 15:6 is preferred.

[0020] The violet pigment of the present invention may be one or more selected from the group consisting of violet pigments such as CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, and CI Pigment Violet 38; among these, CI Pigment Violet 23 is preferred.

[0021] In addition to the pigments described above, the present invention may further contain additional pigments that are commonly used, if necessary.

[0022] The content of the pigment may be in the range of 1 to 30% by weight, preferably 1 to 10% by weight, based on the total weight of the colored photosensitive resin composition.

[0023] It is preferable to use a pigment dispersion in which the pigment is dispersed uniformly with respect to particle size. One example of a method for dispersing the pigment uniformly with respect to particle size is a method in which a pigment dispersant (a2) is added and a dispersion treatment is carried out, and this method makes it possible to obtain a pigment dispersion in which the pigment is dispersed uniformly in the solution.

[0024] Pigment dispersant (a2) The pigment dispersant (a2) is added to deflocculate the pigment and maintain its stability, and any dispersant commonly used in the art can be used without limitation. Preferably, the dispersant contains an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). The acrylic dispersant is preferably prepared by the living control method disclosed in Korean Patent Publication No. 2004-0014311. Commercially available acrylate dispersants prepared by the living control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2002, DISPER BYK-2003, DISPER BYK-2004, DISPER BYK-2005, DISPER BYK-2006, DISPER BYK-2007, DISPER BYK-2008, DISPER BYK-2009, DISPER BYK-2010, DISPER BYK-2011, DISPER BYK-2012, DISPER BYK-2013, DISPER BYK-2014, DISPER BYK-2015, DISPER BYK-2016, DISPER BYK-2017, DISPER BYK-2018, DISPER BYK-2019 ... Examples include BYK-2070 and DISPER BYK-2150.

[0025] The acrylic dispersants exemplified above can be used alone or in combination of two or more. As the pigment dispersant (a2), in addition to the acrylic dispersants, other resin-type pigment dispersants can also be used. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, particularly oily dispersants such as polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamidophosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or amides formed by the reaction of polyesters having free carboxyl groups with poly(lower alkyleneimines) or salts thereof; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone; polyesters; modified polyacrylates; addition products of ethylene oxide / propylene oxide; and phosphate esters.

[0026] Commercially available resin-type dispersants include cationic resin dispersants such as those available from BYK Chemie under the trade names DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-164. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubirzol trade names: SOLSPERS-24000, SOLSPERS-32550 , NBZ-4204 / 10; Kawaken Fine Chemicals Co., Ltd., trade names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto Co., Inc., trade names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Kyoeisha Chemical Co., Ltd., trade names: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. In addition to the acrylic dispersants, other resin-type pigment dispersants can be used alone or in combination of two or more, and may also be used in combination with acrylic dispersants.

[0027] The amount of the pigment dispersant (a2) used is 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, per 100 parts by weight of the solid content of the pigment (a1) used. When the content of the pigment dispersant (a2) satisfies the above range, it can be advantageous in terms of viscosity and pigment atomization, and can reduce the possibility of problems such as gelation after dispersion occurring.

[0028] Dispersing agent (a3) The dispersing agent (a3) ​​is a preparation that disperses the pigment into fine particles and prevents re-aggregation, and is effective in forming a colored layer with a high contrast ratio and excellent transmittance.

[0029] Examples of dispersing aids that can be used in the present invention include 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis{[2-(diethylamino)ethyl]amino}anthra-9,10-quinone, 1,8-bis(benzamido)anthraquinone, 1,4-bis{[2-(4-hydroxyphenyl)ethyl]amino}anthra-9,10-quinone, 1,4-bis{[2-(dimethylamino)ethyl]amino}-5,8-dihydroxyanthra-9,10-quinone, ...diamino-4,5-dihydroxyanthraquinone, 1,5-bis{[2-(diethylamino)ethyl]amino}anthra-9,10-quinone, 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis{[2-(diethylamino)ethyl]amino}anthra-9,10-quinone, 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis{[2-(diethylamino)ethyl]amino}anthra-9,10-quinone, 1,8-diamino-4,5-dihydroxyan hydroxy-4-[4-(2-hydroxyethyl)anilino]-5-nitroanthra-9,10-quinone, 1,4-dihydroxyanthraquinone, 1,4-bis(4-butylanilino)-5,8-dihydroxyanthraquinone, 4'-(4-hydroxy-1-anthraquinonylamino)-acetanilide, 1,4-bis[(2,6-diethyl-4-methylphenyl)amino]anthraquinone, 1,4-bis(butylamino)-9,10-anthracenedione, 1,4-bis(4-butylanilino) 1,4-bis(2,6-diethyl-4-methylanilino)anthraquinone, 2,2'-(9,10-dioxoanthracene-1,4-diyldiimino)bis(5-methylsulfonate), 1-anilino -4-hydroxyanthraquinone, 1-hydroxy-4-[(4-methylphenyl)amino]-9,10-anthracenedione, 1,4-bis(para-tolylamino)anthraquinone, 1-amino-4-phenylaminoanthraquinone, N-[4-[(4-hydroxy-anthraquinon-1-yl)amino]phenyl]acetamide, 1-(methylamino)-4-(4-methylanilino)anthracene-9,10-dione, and 1,4,5,8-tetrahydroxyanthraquinone.

[0030] In addition to the above dispersing aids, commercially available dispersing aids may be further included as needed, such as Lubrizol's SOLSPERSE-5000, SOLSPERSE-12000, and SOLSPERSE-22000, BYK's BYK-SYNERGIST 2100 and BYK-SINERGIST 2105, and BASF's EFKA-6745 and EFKA-6750.

[0031] The dispersing aid is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the pigment in the colorant. When the content of the dispersing aid satisfies this range, the inherent color of the pigment dispersion may be altered, and discoloration due to hard baking during the manufacturing process of the colored layer may be reduced.

[0032] Dispersion solvent (a4) The dispersion solvent (a4) is not particularly limited, and various organic solvents used in the relevant field can be used.

[0033] Specific examples 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; propylene glycol monomethyl ether acetate; alkylene glycol alkyl ether acetates such as 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. Preferably, alkylene glycol alkyl ether acetates, ketones, and esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate can be used.

[0034] The dispersion solvents can be used alone or in combination of two or more.

[0035] The dispersion solvent is contained in an amount of 60 to 90 wt %, preferably 70 to 85 wt %, based on the total weight of the pigment dispersion. When the content of the dispersion solvent satisfies this range, the pigment dispersion may be less likely to suffer from poor storage stability.

[0036] Dispersion resin (a5) The dispersing resin (a5) acts as a dispersion medium for the pigment dispersion (A) and can be added selectively, and a better pigment dispersion can be produced by mixing the dispersing resin (a5) with the dispersing agent (a2) rather than using it alone. Any dispersing resin can be used without limitation as long as it can act as a dispersion medium, but in consideration of the developability of the colored photosensitive resin composition produced from the pigment dispersion, it is preferable for the resin to have an acid value so as to be soluble in an alkaline developer.

[0037] Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of acrylic polymer, and is usually determined by titration with an aqueous potassium hydroxide solution. Dispersion resins with an acid value can be produced by copolymerizing a compound (b1) having a carboxyl group and an unsaturated bond with a compound (b2) having an unsaturated bond copolymerizable with the compound (b1).

[0038] Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of the dicarboxylic acids; and mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, among which acrylic acid and methacrylic acid are preferred. In the present invention, (meth)acrylate refers to acrylate, methacrylate, or both.

[0039] The compounds exemplified as the compound (b1) can be used either alone or in combination of two or more. Examples of the compound (b2) having an unsaturated bond copolymerizable with the compound (b1) include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, 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, and p-vinylbenzyl glycidyl ether; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6] Alicyclic (meth)acrylates such as decan-8-yl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methyl Examples of suitable oxetane compounds include, but are not limited to, N-substituted maleimide compounds such as N-methylphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl(meth)acrylamide; and unsaturated oxetane compounds such as 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane.

[0040] The compounds exemplified as the compound (b2) can be used either alone or in combination of two or more.

[0041] The dispersing resin is contained in an amount of 5 to 70 parts by weight, preferably 10 to 60 parts by weight, per 100 parts by weight of the pigment solid content in the colorant. When the content of the dispersing resin satisfies the above range, the dispersing resin may increase the viscosity or reduce the possibility of the pigment dispersion being atomized.

[0042] dye (a6) A dye may be selectively included in the (A) pigment dispersion, and any dye can be used without limitation as long as it is soluble in an organic solvent. It is preferable to use a dye that is soluble in an organic solvent and can ensure reliability, such as solubility in an alkaline developer, heat resistance, and solvent resistance. The dye may be selected from acid dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof. Azo-, xanthene-, or phthalocyanine-based acid dyes and their derivatives may also be selected.

[0043] Preferably, the dye is a compound classified as a dye in the Color Index (published by The Society of Dyers and Colourists) or a known dye described in Dyeing Notes (Shikisensha).

[0044] Specific examples of the dye include: As a CI solvent dye, CI Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 177, 162, 163, 167 and 189; CI Solvent Red 8, 45, 49, 111, 122, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245 and 247; CI Solvent Orange 2, 7, 11, 15, 26, 56, 77 and 86; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, and 60; CI Solvent Blue 35, 37, 59 and 67; Examples of dyes include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

[0045] Also, as a CI acid dye, 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, 1 57, 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 Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 97, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 160, 172, 176, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 240, 241, 242, 243, 83, 195, 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 and 426; 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 34; Dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

[0046] Furthermore, as a CI direct dye, 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 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 Orange 26, 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, 17 0, 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; Dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

[0047] Also, as a CI mordant dye, CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65; CI 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 and 95; CI Mordant Orange 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 Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; Dyes such as CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53 are included.

[0048] CI Disperse Yellow 51, 54, 76; Disperse dyes such as CI Disperse Violet 26 and 27, CI Reactive Yellow 2, 76, 116; Examples include CI reactive dyes such as CI Reactive Orange 16.

[0049] (B) Alkali-soluble resin The alkali-soluble resin (B) must be soluble in the solvent of the present invention and reactive to light or heat. Furthermore, any acrylic copolymer can be used without particular limitations as long as it functions as a binder resin for the colorant and is soluble in an alkaline developer.

[0050] The alkali-soluble resin may be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer. The carboxyl group-containing monomer may be, for example, an unsaturated carboxylic acid, such as an unsaturated polycarboxylic acid having one or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. The unsaturated monocarboxylic acid may be, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, or cinnamic acid. The unsaturated dicarboxylic acid may be, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, or mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, specifically, maleic anhydride, itaconic anhydride, or citraconic anhydride. The unsaturated polycarboxylic acid may be a mono(2-methacryloyloxyalkyl) ester, such as mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) phthalate, or mono(2-methacryloyloxyethyl) phthalate. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends, such as ω-carboxypolycaprolactone monoacrylate or ω-carboxypolycaprolactone monomethacrylate. The carboxyl group-containing monomers may be used alone or in combination of two or more. Specific examples of other monomers copolymerizable with the carboxyl group-containing monomer include 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;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, cyclohexane unsaturated carboxylic acid esters such as 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, and 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, and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, and allyl Examples of suitable monomers include unsaturated ethers such as glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and macromonomers having monoacryloyl or monomethacryloyl groups at the ends of the polymer molecular chains of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These monomers can be used singly or in combination.

[0051] Therefore, the alkali-soluble resin may be, for example, a (meth)acrylic acid / methyl (meth)acrylate copolymer, a (meth)acrylic acid / benzyl (meth)acrylate copolymer, a (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymer, a (meth)acrylic acid / methyl (meth)acrylate / polystyrene macromonomer copolymer, a (meth)acrylic acid / methyl (meth)acrylate / polymethyl (meth)acrylate macromonomer copolymer, a (meth)acrylic acid / benzyl (meth)acrylate / polystyrene macromonomer copolymer, a (meth)acrylic acid / benzyl (meth)acrylate / polymethyl (meth)acrylate macromonomer copolymer, a (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate (meth)acrylate / polystyrene macromonomer copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / polymethyl (meth)acrylate macromonomer copolymer, (meth)acrylic acid / styrene / benzyl (meth)acrylate / N-phenylmaleimide copolymer, (meth)acrylic acid / mono(2-acryloyloxy)succinate / styrene / benzyl (meth)acrylate / N-phenylmaleimide copolymer, (meth)acrylic acid / mono(2-acryloyloxyethyl)succinate / styrene / allyl (meth)acrylate / N-phenylmaleimide copolymer, and (meth)acrylic acid / benzyl (meth)acrylate / N-phenylmaleimide / styrene / glycerol mono(meth)acrylate copolymer may also be used. The (meth)acrylate refers to acrylate or methacrylate.

[0052] Of the alkali-soluble resins, (meth)acrylic acid / benzyl (meth)acrylate copolymer, (meth)acrylic acid / benzyl (meth)acrylate / styrene copolymer, (meth)acrylic acid / methyl (meth)acrylate copolymer, and (meth)acrylic acid / methyl (meth)acrylate / styrene copolymer are preferably used.

[0053] The alkali-soluble resin should have a polystyrene-equivalent weight-average molecular weight of 5,000 to 50,000, preferably 8,000 to 40,000, and more preferably 10,000 to 30,000, as measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent. When the weight-average molecular weight of the alkali-soluble resin falls within the range of 5,000 to 50,000, the resin exhibits improved coating hardness, excellent film retention, and good solubility of unexposed areas in a developer and improved resolution. Furthermore, the resin has an acid value of 50 to 150 (mgKOH / g), preferably 60 to 140, and more preferably 80 to 130. Within this acid value range, the alkali-soluble resin exhibits improved solubility in a developer, easily dissolving unexposed areas and increasing sensitivity, resulting in a pattern remaining in the exposed areas during development, improving film retention.

[0054] The alkali-soluble resin may be contained in an amount of 0.05 to 30 wt %, preferably 1 to 10 wt %, based on the total weight of the colored photosensitive resin composition. When this range is satisfied, problems such as a decrease in film retention rate and a decrease in reliability are less likely to occur, and pattern formation may be easier.

[0055] (C) Photopolymerizable compound The (C) photopolymerizable compound is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator upon irradiation with light, and may be a monofunctional or difunctional or higher functional polymerizable compound depending on the number of functional groups.

[0056] Specific examples of the monofunctional monomer include, but are not limited to, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

[0057] Specific examples of the bifunctional or higher functional monomer 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, butylene glycol dimethacrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, or propoxylated neopentyl glycol diacrylate, and tri- or higher functional monomers include, but are not limited to, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, glyceryl propoxylate triacrylate, or isocyanurate triacrylate.

[0058] In particular, the photopolymerizable compound of the present invention preferably contains 1 to 3 ethylene oxide groups. This is because if the compound contains four or more ethylene oxide groups, the developability will be increased, the degree of film scraping will increase, and the surface roughness may become poor. If the compound does not contain ethylene oxide groups, the developability will rapidly decrease, resulting in the problem of residue generation during pattern formation. In contrast, if the compound contains 1 to 3 ethylene oxide groups, the surface area that can act as a hydrophilic group is optimal, so the residue problem does not occur, and the degree of film scraping by the developer is significantly reduced compared to when the compound contains four or more ethylene oxide groups, thereby improving surface roughness.

[0059] Specifically, compounds having a structure such as that of the following chemical formula 1 can be preferably used, and in particular, a structure in which the core structure of the following chemical formula 1 contains 1 to 3 ethylene oxide groups is most preferred. [Chemical formula 1] [ka]

[0060] The photopolymerizable compound is contained in an amount of 1 to 30 wt %, and more preferably 1 to 10 wt %, based on the total weight of the colored photosensitive resin composition. When the photopolymerizable compound is contained in such a range, the strength and smoothness of the pixel portion can be improved.

[0061] (D) Photopolymerization initiator The photopolymerization initiator (D) in the present invention is a compound that generates radicals capable of initiating polymerization of the polyfunctional monomer of the photopolymerizable compound upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, or X-rays. Representative examples of such photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, biimidazole-based compounds, triazine-based compounds, oxime ester-based compounds, and thioxanthone-based compounds. In the present invention, the photopolymerization initiators can be used alone or in combination, with one or more oxime ester-based or triazine-based compounds being preferred. In particular, for photoresists for solid-state imaging, patterns with a taper angle close to 90 degrees must be realized, so the degree of cure of the lower and upper portions must be similar. To achieve this effect, it is preferred to include one or more photopolymerization initiators selected from triazine-based or oxime ester-based compounds, which have excellent surface curing capabilities.

[0062] Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

[0063] Examples of the benzophenone compounds include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0064] 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, and imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups. Of these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably used.

[0065] 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.

[0066] Examples of the oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), and 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime).

[0067] Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0068] In addition, the photopolymerization initiator (D) may further contain a photopolymerization initiation aid (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. By containing the photopolymerization initiation aid (d1), the colored photosensitive resin composition of the present invention can further increase its sensitivity and improve productivity.

[0069] The photopolymerization initiation aid (d1) is preferably, 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.

[0070] As the amine compound, it is preferable to use an aromatic amine compound. Specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, 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 can be used.

[0071] The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof 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.

[0072] Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

[0073] The (D) photopolymerization initiator is contained in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is contained within the above-mentioned range, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, which is preferable because it improves productivity and allows high resolution to be maintained. Furthermore, the strength of the pixel portion formed using the composition under the above-mentioned conditions and the smoothness of the surface of the pixel portion can be improved.

[0074] The photopolymerization initiation assistant (d1) can be contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the photopolymerization initiator. When the content of the photopolymerization initiation assistant (d1) in the total weight of the photopolymerization initiator satisfies the above range, it is possible to reduce the possibility of a decrease in sensitivity to dyes and short-circuiting of patterns during the development process.

[0075] Furthermore, when the photopolymerization initiation aid (d1) is further used, the photopolymerization initiation aid (d1) is contained in an amount of 0.1 to 40 wt %, preferably 1 to 30 wt %, based on the total weight of the solids content of the colored photosensitive resin composition of the present invention, relative to the content of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the amount of the photopolymerization initiation aid (d1) used is within the above-mentioned range of 0.1 to 40 wt %, the sensitivity of the colored photosensitive resin composition is further increased, thereby providing an effect of improving the productivity of color filters formed using the composition.

[0076] (E) Solvent The solvent is not particularly limited as long as it dissolves the colored photosensitive resin composition, and particularly preferred are ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.Specifically, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, and dipropylene glycol dibutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol alcohols such as alcohol and glycerin; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomer Examples of the solvent include ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and esters such as γ-butyrolactone. The solvent can be used alone or in combination of two or more selected from the group consisting of the above-mentioned solvents.In addition, from the viewpoint of coatability and drying property, the boiling point must be 100 to 200°C, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate are preferred.

[0077] The solvent may be contained in an amount of 10 to 60% by weight, preferably 20 to 40% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent is contained in this range, good coatability can be achieved when the composition is coated using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (or die coater), or inkjet.

[0078] Additive (F) In addition to the above-described components, the colored photosensitive resin composition of the present invention may also contain additives (F) such as fillers, other polymer compounds, curing agents, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents, as needed by those skilled in the art, within the scope of the object of the present invention.

[0079] The filler may be specifically glass, silica, alumina, etc., but is not limited thereto.

[0080] Specific examples of the other polymer compound that can be used include curable 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, but are not limited thereto.

[0081] The curing agent is used to enhance deep curing and mechanical strength, and specific examples of the curing agent that can be used include, but are not limited to, epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds. Specific examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac 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; epoxidized butadiene (co)polymers; epoxidized isoprene (co)polymers; glycidyl (meth)acrylate (co)polymers; and triglycidyl isocyanurate. Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane, but are not limited thereto.

[0082] The curing agent may be used in combination with a curing auxiliary compound that enables ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Specific examples of the curing auxiliary compound that can be used include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. The carboxylic anhydrides may be commercially available epoxy resin curing agents. Examples of commercially available epoxy resin curing agents include those under the trade name (ADEKA HARDNER EH-700) (manufactured by ADEKA Kogyo Co., Ltd.), the trade name (RIKACID HH) (manufactured by New Japan Chemical Co., Ltd.), and the trade name (MH-700) (manufactured by New Japan Chemical Co., Ltd.).

[0083] The curing agents and curing auxiliary compounds exemplified above can be used alone or in combination of two or more.

[0084] 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, and 3-isocyanatopropyltriethoxysilane, and these compounds may be used alone or in combination.

[0085] The adhesion promoter is contained in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on the solid content of the composition.

[0086] The ultraviolet absorber may specifically be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, or the like, but is not limited thereto.

[0087] The anti-aggregating agent may be, for example, sodium polyacrylate, but is not limited thereto.

[0088] <Color filters, solid-state imaging devices and display devices> The present invention provides a color filter manufactured using the colored photosensitive resin composition, and a solid-state imaging device and a display device including the color filter. The colored photosensitive resin composition can be coated on a substrate, photocured, and developed to form a pattern.

[0089] First, the colored photosensitive resin composition is applied onto a substrate or onto a layer of the solid content of the photosensitive resin composition, and then heated and dried to remove volatile components such as solvents, thereby obtaining a smooth coating film.

[0090] Coating methods include spin coating, casting, roll coating, slit-and-spin coating, and slit coating. After coating, the coating is prebaked or dried under reduced pressure and then heated to volatilize volatile components such as the solvent. The heating temperature is 70 to 200°C, preferably 80 to 130°C. The coating film has a thickness of approximately 0.5 to 8 μm after drying. To form the desired pattern, the coating film is irradiated with ultraviolet light through a mask. The entire exposed area must be uniformly irradiated with parallel light, and it is preferable to use a device such as a mask aligner or stepper to ensure accurate alignment between the mask and the substrate. The ultraviolet light irradiation hardens the irradiated area. Examples of ultraviolet light that can be used include g-rays (wavelength: 436 nm), h-rays, KrF (248 nm), and i-rays (wavelength: 365 nm). The amount of ultraviolet light can be appropriately selected as needed, and is not limited by this in the present invention. The cured coating film is brought into contact with a developer to dissolve the unexposed areas and develop the film, thereby obtaining a cured product having the desired pattern shape.

[0091] The present invention also provides a solid-state imaging device or a display device including the color filter. [Example]

[0092] Preferred examples, comparative examples, and experimental examples are presented below to aid in understanding the present invention. However, these examples, comparative examples, and experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the examples, comparative examples, and experimental examples are possible within the scope of the scope and technical idea of ​​the present invention, and it is natural that such changes and modifications also fall within the scope of the appended claims.

[0093] Manufacturing example Manufacturing Example 1. Pigment Dispersion 1-1 Pigment Dispersion 1-1 was produced by mixing and dispersing 10 parts by weight of CI Pigment Blue 15:6 (Grade I) as a pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0094] Manufacturing Example 2. Pigment Dispersion 1-2 Pigment Dispersion 1-2 was produced by mixing and dispersing 10.0 parts by weight of CI Pigment Blue 15:6 (Grade II) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0095] Production Example 3. Pigment Dispersion 1-3 Pigment Dispersion 1-3 was produced by mixing and dispersing 10.0 parts by weight of CI Pigment Blue 15:6 (Grade III) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0096] Production Example 4. Pigment Dispersion 1-4 Pigment Dispersion 1-4 was produced by mixing and dispersing 10.0 parts by weight of CI Pigment Blue 15:6 (Grade IV) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0097] Production Example 5. Pigment Dispersion 1-5 Pigment Dispersion 1-5 was produced by mixing and dispersing 10.0 parts by weight of CI Pigment Blue 15:6 (Grade V) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0098] Production Example 6. Pigment Dispersion 1-6 Pigment Dispersion 1-6 was produced by mixing and dispersing 12.0 parts by weight of CI Pigment Blue 15:6 (Grade VI) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0099] Production Example 7. Pigment Dispersion 1-7 Pigment Dispersion 1-7 was produced by mixing and dispersing 12.0 parts by weight of CI Pigment Blue 15:6 (Grade VII) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0100] Production Example 8. Pigment Dispersion 1-8 Pigment Dispersion 1-8 was produced by mixing and dispersing 12.0 parts by weight of CI Pigment Blue 15:6 (Grade VIII) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0101] Production Example 9. Pigment Dispersion 1-9 Pigment Dispersion 1-9 was produced by mixing and dispersing 12.0 parts by weight of CI Pigment Blue 15:6 (Grade IX) as the pigment, 5.0 parts by weight of DISPERBYK-2001 (BYK) as the pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as the solvent using a bead mill for 12 hours. The particle size of the colorant was measured using an ELS-Z2 analyzer manufactured by Otsuka Electronics Co., Ltd. after diluting it with propylene glycol monomethyl ether acetate so that the pigment concentration was in the range of 1 to 6% by weight. The volume average particle size was measured from the volume particle size distribution obtained and is shown in the table below.

[0102] [Table 1]

[0103] Synthesis Example Synthesis Example 1. Alkali-soluble resin 2-1 A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was charged with 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, 13.0 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecanethiol, and the atmosphere was purged with nitrogen. The reaction mixture was then stirred, the temperature was raised to 110°C, and the reaction was carried out for 6 hours. The acid value of the solid content of the alkali-soluble resin synthesized in this manner was 95.8 mg KOH / g, and the weight-average molecular weight (Mw) measured by GPC was approximately 14,200.

[0104] Examples 1 to 5 and Comparative Examples 1 to 6 Production of colored photosensitive resin composition for solid-state imaging devices Colored photosensitive resin compositions were produced according to the compositions and contents (unit: parts by weight) shown in Table 2 below.

[0105] [Table 2]

[0106] -1-1 to 1-9: Pigment dispersions according to Production Examples 1-1 to 1-9 -2-1: Alkali-soluble resin according to Synthesis Example 1 -3-1: A-TMPT (Shin-Nakamura Co., Ltd.) -3-2: A-TMPT-3EO (Shin-Nakamura Co., Ltd.) -3-3: A-TMPT-9EO (Shin-Nakamura Co., Ltd.) -4-1: OXE-01 (BASF) -5-1: SH-8400 (Dow Corning Korea Co., Ltd.) -6-1: Propylene glycol monomethyl ether acetate (KH NEOCHEM CO.LTD.)

[0107] Experimental Example 1: Evaluation of pattern straightness and residue In a clean room at 23°C, the colored photosensitive resin compositions of the Examples, Comparative Examples, and Reference Examples were applied by spin coating onto the surface of a glass substrate (manufacturer: Corning Incorporated, product name: No. 1737, thickness: 0.7 mm). The substrate was then placed on a heating plate and maintained at 100°C for 3 minutes to form a thin film. The formed colored photosensitive resin layer was cooled to 23°C, and then selectively exposed to i-rays (wavelength 365 nm) using a photomask. An ultra-high pressure mercury lamp was used as the i-ray light source, and the irradiation dose was 150 mJ / cm. 2 The photomask used was a photomask for forming color pixels in the form of lines and dots with line widths of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm. The selectively exposed colored photosensitive resin layer was then immersed in a developer solution containing 0.04 wt% tetramethylammonium hydroxide at 23°C for development. After rinsing with pure water, the layer was post-baked at 220°C for 90 seconds to form a colored pattern. The thickness of the resulting colored pattern was 0.8 μm, and the minimum line width (resolution) was 1 μm. The linearity and residue of the resulting colored pattern were observed and evaluated according to the following criteria.

[0108] <Evaluation criteria for pattern straightness and residue> 1: Severe delinquency 2: Bad 3: Normal 4: Good 5: Very good

[0109] Experimental example 2: Surface roughness evaluation In a clean room at 23°C, the colored photosensitive resin compositions of the Examples, Comparative Examples, and Reference Examples were applied by spin coating onto the surface of a glass substrate (manufacturer: Corning Incorporated, product name: No. 1737, thickness: 0.7 mm). The substrate was then placed on a heating plate and maintained at a temperature of 100°C for 3 minutes to form a thin film. The formed colored photosensitive resin layer was cooled to 23°C, and then selectively exposed to i-rays (wavelength 365 nm) using a photomask. An ultra-high pressure mercury lamp was used as the i-ray light source, and the irradiation dose was 150 mJ / cm. 2 The selectively exposed colored photosensitive resin layer was then immersed in an aqueous solution containing 0.04% by weight of tetramethylammonium hydroxide as a developer at 23°C for development. The average roughness (Ra) was then measured using an atomic force electron microscope (manufacturer: Park System, model name: NX10) in non-contact mode. The average roughness was evaluated according to the following criteria.

[0110] <Surface roughness evaluation standard - Ra value> Before 40pm: Yes Between 40pm and 50pm: △ Over 50pm: ×

[0111] Experimental Example 3: Evaluation of viscosity over time The viscosity of the colored photosensitive resin compositions of the Examples, Comparative Examples, and Reference Examples at 25°C immediately after production and after storage for 5 months at a constant temperature of 10°C were measured using an E-type viscometer (Brookfield, model name: LVDV3T) at a rotation speed of 50 rpm. The viscosity on the day of production of the colored composition was defined as the initial viscosity (V1: cP) and the viscosity after storage for 5 months at a constant temperature (V2: cP), and the dispersion stability was evaluated according to the following criteria.

[0112] <Evaluation criteria for viscosity over time - viscosity stability> (V2-V1) x 100% <V1×0.1×100%:○ V1×0.1×100%<(V2-V1)×100% <V1×0.13×100%:△ (V2-V1)×100%>V1×0.13×100%:×

[0113] [Table 3]

[0114] In the present invention, blue and violet pigments were used to prepare pigment dispersions having a volume average particle size in the range of 15 to 60 nm, and colored photosensitive resin compositions were prepared using these pigment dispersions. Through these experimental examples, the effect of improving surface roughness, the degree of improvement in pattern straightness, and the viscosity stability over time of colored photosensitive resin compositions prepared using pigment dispersions having a volume average particle size in the range of 15 to 60 nm were confirmed.

[0115] When a colored photosensitive resin composition is prepared using a pigment dispersion having a volume average particle size in the range of 15 to 60 nm, as in Examples 1 to 5, it is confirmed that the effects of improving surface roughness and pattern straightness are all excellent, and that viscosity stability over time is also maintained appropriately. In contrast, when the volume average particle size is smaller than the preferred range, as in Comparative Example 1, it is confirmed that the viscosity stability over time is poor due to aggregation, in which pigment particles clump together. In contrast, when the volume average particle size is larger than the preferred range, as in Comparative Examples 2 to 4, it is confirmed that the viscosity stability over time is maintained favorably, but the pigment particles are unable to penetrate into the composition, significantly reducing the effect of improving surface roughness.

[0116] In addition, when a photopolymerizable compound having 1 to 3 added ethylene oxide groups is used in the present invention, the problem of residue does not occur and the effect of improving surface roughness can be maximized. However, when a colored photosensitive resin composition is prepared using a photopolymerizable compound having an ethylene oxide group in a range outside the range of the present invention, as in Reference Examples 1 and 2, it has been confirmed that the effect of improving the surface roughness and residue problems is reduced.

Claims

1. A colored photosensitive resin composition comprising (A) a pigment dispersion, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, The viscosity of the colored photosensitive resin composition satisfies the following formula 1: A color filter produced from the colored photosensitive resin composition has an average surface roughness (Ra) of less than 40 pm. [Formula 1] (V2-V1) x 100% < V1 x 0.1 x 100% [In formula 1, V1 represents the viscosity of the colored photosensitive resin composition on the day of production, V2 represents the viscosity of the colored photosensitive resin composition after storage at a constant temperature of 10°C for 5 months.

2. 2. The colored photosensitive resin composition according to claim 1, wherein the pigment dispersion liquid (A) contains a blue pigment or a violet pigment.

3. 3. The colored photosensitive resin composition according to claim 2, wherein the blue pigment comprises one or more selected from the group consisting of C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and C.I. Pigment Blue 60.

4. 3. The colored photosensitive resin composition according to claim 2, wherein the violet pigment comprises one or more pigments selected from the group consisting of C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, and C.I. Pigment Violet 38.

5. Based on the total weight of the colored photosensitive resin composition, 1 to 30% by weight of pigment, (B) 0.05 to 30% by weight of an alkali-soluble resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) 0.1 to 20% by weight of a photopolymerization initiator, and 2. The colored photosensitive resin composition according to claim 1, further comprising 10 to 60% by weight of a solvent (E).

6. 2. The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (C) contains 1 to 3 ethylene oxide groups.

7. 2. The colored photosensitive resin composition according to claim 1, wherein the (D) photopolymerization initiator comprises at least one selected from the group consisting of oxime-based and triazine-based photopolymerization initiators.

8. A color filter produced using the colored photosensitive resin composition according to any one of claims 1 to 7.

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

10. A display device comprising the color filter according to claim 8.

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