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

Abstract

To provide a colored photosensitive resin composition which exhibits superior developability, is free from residue during color pattern formation, offers superior adhesiveness and pattern linearity, and enables improved pigment dispersibility.SOLUTION: A colored photosensitive resin composition comprises a colorant, an alkali-soluble resin containing a repeating unit of a specific structure, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored photosensitive resin composition is used to form a color filter, as well as an image display device and a solid-state imaging element equipped with the color filter.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, and more particularly to a colored photosensitive resin composition that has excellent developability and adhesion and can also improve pigment dispersibility, and is capable of forming an elaborate pattern with high resolution, a color filter formed using the same, and an image display device equipped with the color filter. [Background technology]

[0002] A solid-state imaging device is a device that converts an image captured using optical energy into electrical information, and may include a color filter below the lens. For example, a CMOS Image Sensor (CIS) uses a fine-pitch color filter that is patterned at a higher resolution than the color filters that correspond to the pixels of a typical display device. The color filter of a CIS usually has a color pattern of the three primary colors, red (R), green (G), and blue (B), and is responsible for separating transmitted light into the three primary colors.

[0003] In recent years, as the pixel density of color filters used in this type of image sensor increases, the pigment content in colored photosensitive resin compositions has increased, which has led to problems such as a decrease in the degree of cure of the colored photosensitive resin composition, making it difficult to ensure pattern characteristics, and generating residues.

[0004] Therefore, there has been a demand for the development of a colored photosensitive resin composition that has high pigment dispersibility and excellent patterning properties such as developability and adhesion, as well as residue or film remaining property and linearity, so as to enable fine patterning.

[0005] Korean Patent Publication No. 10-2009-0072754 discloses a composition for color filters containing a pigment and a binder resin, but it is not suitable for application to the color filters for the above-mentioned high-resolution solid-state imaging devices. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a colored photosensitive resin composition which is excellent in developability and adhesion, and which can also improve pigment dispersibility, and which is capable of forming an elaborate pattern with high resolution.

[0007] Another object of the present invention is to provide a colored pattern formed using the colored photosensitive resin composition.

[0008] It is still another object of the present invention to provide a color filter including the colored pattern.

[0009] A further object of the present invention is to provide an image display device equipped with the color filter.

[0010] A still further object of the present invention is to provide a solid-state imaging device equipped with the above color filter. [Means for solving the problem]

[0011] On the other hand, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin comprises a first repeating unit represented by the following chemical formula 1 and a second repeating unit represented by the following chemical formula 2:

[0012] [ka]

[0013] In the above formula, R 1 ~R 9 are each independently hydrogen, halogen, or C1-C 10 or C1-C 10 is an alkoxy group of the formula R 10 is hydrogen or a methyl group, R11 is hydrogen or a methyl group, R 12 is C1-C 10 is an alkylene group of the formula R 13 is a C3-C7 alkylene group, n is an integer of 1 to 20.

[0014] In one embodiment of the present invention, R 1 ~R 9 is hydrogen, R 12 is a C1-C3 alkylene group, R 13 is a C3-C5 alkylene group, n may be an integer of 1 to 5.

[0015] In one embodiment of the present invention, the first repeating unit represented by Chemical Formula 1 may be contained in an amount ranging from 10 to 80 mol % relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

[0016] In one embodiment of the present invention, the second repeating unit represented by Chemical Formula 2 may be contained in an amount ranging from 10 to 70 mol % relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

[0017] On the other hand, the present invention provides a colored pattern formed using the colored photosensitive resin composition.

[0018] On the other hand, the present invention provides a color filter including the colored pattern.

[0019] On the other hand, the present invention provides an image display device comprising the above-mentioned color filter.

[0020] On the other hand, the present invention provides a solid-state imaging device comprising the above-described color filter.

[0021] In one embodiment of the present invention, the solid-state imaging device may include a CMOS image sensor. [Effects of the Invention]

[0022] The colored photosensitive resin composition according to the present invention contains an alkali-soluble resin that includes a first repeating unit containing a phenoxybenzyl group of a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group. This allows the composition to have excellent developability with TMAH (tetramethyl ammonium hydroxide), leaving no residue when a colored pattern is formed, and also provides excellent adhesion and linearity of the pattern, as well as improved pigment dispersibility. DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention will now be described in more detail.

[0024] One embodiment of the present invention relates to a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the alkali-soluble resin (B) comprises a first repeating unit containing a phenoxybenzyl group of a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group.

[0025] Hereinafter, each component of the colored photosensitive resin composition according to one embodiment of the present invention will be described in detail.

[0026] [Colorant (A)] In one embodiment of the present invention, the colorant (A) may be an organic pigment, an inorganic pigment, or a dye that is commonly used in this field.

[0027] The organic pigment may be any of various pigments used in printing inks, inkjet inks, etc., and specific examples thereof include water-soluble phthalocyanine 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, and diketopyrrolopyrrole pigments.

[0028] The pigment may be subjected to, as necessary, a resin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, a grafting treatment onto the pigment surface using a polymer compound or the like, a microparticle treatment using a sulfuric acid microparticle treatment or the like, a washing treatment using an organic solvent or water to remove impurities, a treatment to remove ionic impurities using an ion exchange method or the like, or the like.

[0029] Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples include oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black.

[0030] As the pigment used in the present invention, organic pigments or inorganic pigments generally used in the relevant field may be used, and these may be used alone or in combination of two or more kinds.

[0031] In particular, the pigment may be a compound classified as a pigment in the Colour Index (published by The Society of Dyers and Colourists). More specifically, pigments having the following Colour Index (CI) numbers may be used, but are not necessarily limited to these.

[0032] CI 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 CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71 CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264, and 277 CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38 CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76 CI Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62, and 63 CI Pigment Brown 28 CI Pigment Black 1 and 7, etc. Among the CI pigment pigments exemplified above, a pigment selected from CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 may be preferably used.

[0033] 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 is added to the pigment for dispersion treatment, and this method makes it possible to obtain a pigment dispersion in which the pigment is dispersed uniformly in the solution.

[0034] Examples of the pigment dispersant include cationic, anionic, nonionic, cationic, polyester, and polyamine surfactants, and these may be used alone or in combination of two or more.

[0035] Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other examples of the surfactant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemicals), and PB 821 (manufactured by Ajinomoto Co., Inc.).

[0036] The pigment dispersant is typically used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 parts by weight, per 1 part by weight of the pigment. When the pigment dispersant is used in the amount described above, it is preferable because a dispersed pigment with a uniform particle size can be obtained.

[0037] The dye may be used without any particular limitation as long as it is soluble in an organic solvent. Preferably, a dye may be used that is soluble in an organic solvent and can ensure reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance.

[0038] 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. In addition, azo-, xanthene-, and phthalocyanine-based acid dyes and derivatives thereof may also be selected.

[0039] Preferably, the dyes are compounds classified as dyes within the Colour Index (published by The Society of Dyers and Colourists) or known dyes as described in Dyeing Notes (Irosensha).

[0040] Specific examples of the dye include CI solvent dyes: Yellow dyes such as CI Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; Red dyes such as CI Solvent Red 8, 45, 49, 122, 125, and 130; Orange dyes such as CI Solvent Orange 2, 7, 11, 15, 26, and 56; blue dyes such as CI Solvent Blue 35, 37, 59, and 67; Examples of green dyes include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

[0041] 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, 157, Yellow dyes such as 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; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 207, 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, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 27 red dyes such as 11, 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 CI 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 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, 340; Violet dyes such as CI Acid Violet 6B, 7, 9, 17, and 19; Examples of green dyes include CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

[0042] Also, as a CI direct dye, Yellow dyes such as 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, 141; Red dyes such as 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, 250; Orange dyes such as CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 107; CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171 Blue dyes such as 1, 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 color dyes such as CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104; Examples of green dyes include CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

[0043] Also, as a CI mordant dye, Yellow dyes such as CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; Red dyes such as 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, 95; Orange dyes such as 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; Blue dyes such as 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, 84; Violet color dyes such as CI Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; Examples of green dyes include CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.

[0044] The pigments and dyes may be used in combination of one or more of each.

[0045] The colorant (A) may be contained in an amount of 10 to 70% by weight, preferably 10 to 60% 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 in that the color density of pixels is sufficient during thin film formation, and the lack of non-pixel areas is not reduced during development, and no residue is generated.

[0046] In the present invention, the solid content in the colored photosensitive resin composition means the total amount of the components excluding the solvent.

[0047] [Alkali-soluble resin (B)] In one embodiment of the present invention, the alkali-soluble resin (B) generally has reactivity due to the action of light or heat and alkali-solubility, and acts as a dispersion medium for the coloring material.

[0048] The alkali-soluble resin (B) contains a first repeating unit represented by the following chemical formula 1 and a second repeating unit represented by the following chemical formula 2.

[0049] [ka]

[0050] In the above formula, R 1 ~R 9 are each independently hydrogen, halogen, or C1-C 10 or C1-C 10 is an alkoxy group of the formula R 10 is hydrogen or a methyl group, R 11 is hydrogen or a methyl group, R 12 is C1-C 10 is an alkylene group of the formula R 13 is a C3-C7 alkylene group, n is an integer of 1 to 20.

[0051] As used herein, C1-C 10The alkyl group in this case means a straight-chain or branched hydrocarbon having 1 to 10 carbon atoms, and includes, but is not limited to, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, and decyl.

[0052] As used herein, C1-C 10 The alkoxy group means a linear or branched alkoxy group having 1 to 10 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propanoxy, butoxy, pentoxy, etc.

[0053] As used herein, C1-C 10 The alkylene group means a straight or branched divalent hydrocarbon having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, methylene, ethylene, propylene, butylene, and pentylene.

[0054] As used herein, the term "C3-C7 alkylene group" refers to a linear or branched divalent hydrocarbon having 3 to 7 carbon atoms, including, but not limited to, propylene, butylene, pentylene, and hexylene.

[0055] In one embodiment of the present invention, R 1 ~R 9 is hydrogen and R 12 is a C1-C3 alkylene group, and R 13 is a C3-C5 alkylene group, and n may be an integer of 1-5.

[0056] The first repeating unit represented by Chemical Formula 1 may be introduced using a compound represented by Chemical Formula 3 below.

[0057] [ka]

[0058] In the above formula, R 1 ~R 10 is as defined in Chemical Formula 1 above.

[0059] The alkali-soluble resin (B) contains the first repeating unit represented by Chemical Formula 1, which can improve high-resolution characteristics and fine patterning characteristics. For example, in the first repeating unit, two benzene ring units can be rotatably bonded by an ether bond. Due to the characteristics of this bond structure, the unexposed areas of the substrate can be cleanly removed by a developer. Therefore, a clean, linear colored pattern can be obtained without generating residue in the unexposed areas between the fine-pitch exposed areas.

[0060] The second repeating unit represented by Chemical Formula 2 may be introduced using a compound represented by Chemical Formula 4 below.

[0061] [ka]

[0062] In the above formula, R 11 ~R 13 and n is as defined in Chemical Formula 2 above.

[0063] When the alkali-soluble resin (B) contains the second repeating unit represented by the chemical formula 2, adhesion and developability can be improved, and linearity of the pattern can be ensured.

[0064] In one embodiment of the present invention, the alkali-soluble resin (B) may further contain a third repeating unit derived from a carboxylic acid monomer.

[0065] The carboxylic acid monomer may include an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. For example, the carboxylic acid monomer may include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. These may be used alone or in combination of two or more.

[0066] In one embodiment of the present invention, the third repeat unit may be derived from the carboxylic acid monomer and a reactive monomer that can bond to or copolymerize with the carboxylic acid monomer.

[0067] The reactive monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, or vinyltoluene; an unsaturated carboxylate compound such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, or benzyl methacrylate; an unsaturated aminoalkyl carboxylate compound such as aminoethyl acrylate; an unsaturated glycidyl carboxylate compound such as glycidyl (meth)acrylate; or a vinyl compound such as vinyl acetate or vinyl propionate. vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc.; unsaturated oxetane carboxylate compounds such as 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, and 3-methyl-3-methacryloxyethyloxetane, etc. These may be used alone or in combination of two or more.

[0068] In one embodiment of the present invention, when an unsaturated glycidyl carboxylate compound such as glycidyl (meth)acrylate is used as the reactive monomer capable of bonding with the carboxylic acid monomer, the third repeating unit may be derived from the carboxylic acid monomer and the unsaturated glycidyl carboxylate compound, or may be derived from the carboxylic acid monomer, the unsaturated glycidyl carboxylate compound, and an acid anhydride capable of bonding with the unsaturated glycidyl carboxylate compound.

[0069] Acid anhydride as used herein includes succinic anhydride, methylsuccinic anhydride, (2-dodecen-1-yl)succinic anhydride, phenylsuccinic anhydride, phthalic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, 3,3-dimethylglutaric anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimellitic ... Examples of the acid anhydride include, but are not limited to, maleic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, hexahydrophthalic anhydride, and carbic anhydride. In terms of ease of reactivity, it is preferable to use maleic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, hexahydrophthalic anhydride, and / or carbic anhydride as the acid anhydride, and in particular, trimellitic anhydride, succinic anhydride, and / or hexahydrophthalic anhydride are more preferable.

[0070] In one embodiment of the present invention, the third repeating unit may include repeating units derived from (meth)acrylic acid and glycidyl (meth)acrylate, or may include repeating units derived from (meth)acrylic acid, glycidyl (meth)acrylate, and succinic anhydride. For example, the third repeating unit may include units derived from each of (meth)acrylic acid and glycidyl (meth)acrylate, or may include a structure in which glycidyl (meth)acrylate is bonded to a unit derived from (meth)acrylic acid, or may include a structure in which glycidyl (meth)acrylate and succinic anhydride are sequentially bonded to a unit derived from (meth)acrylic acid.

[0071] The third repeating unit can improve the developability of the alkali-soluble resin and also improve the adhesion of the composition or colored pattern to the substrate.

[0072] The alkali-soluble resin (B) may be a block copolymer in which the first to third repeating units are each repeated at a regular interval, or may be a random copolymer in which these repeating units are repeated at random.

[0073] In one embodiment of the present invention, the first repeating unit may be contained in an amount of 10 to 80 mol %, preferably 20 to 40 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

[0074] In one embodiment of the present invention, the second repeating unit may be contained in an amount of 10 to 70 mol %, preferably 20 to 40 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

[0075] In one embodiment of the present invention, the third repeating unit may be contained in an amount of 10 to 70 mol %, preferably 20 to 50 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

[0076] When the first repeating unit and the second repeating unit are contained within the above-mentioned mole percent ranges, the composition has excellent developability and adhesion, and also has improved pigment dispersibility, making it possible to form a precise pattern with high resolution.

[0077] Furthermore, when the third repeating unit is contained within the above range of mole percent, the developability and adhesion can be improved.

[0078] The alkali-soluble resin may have an acid value in the range of 20 to 100 (KOH mg / g). Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of polymer, and can usually be determined by titration with an aqueous potassium hydroxide solution.

[0079] The weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") of the alkali-soluble resin measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) in terms of polystyrene is preferably in the range of 5,000 to 20,000.

[0080] The double bond equivalent (DBE) of the alkali-soluble resin may be in the range of 300 to 800 g / mol.

[0081] Within the above-mentioned ranges of acid value, weight average molecular weight, and double bond equivalent, excellent developability and pattern characteristics can be obtained, and the dispersibility of the pigment can be improved.

[0082] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.0 to 6.0, and more preferably 1.5 to 6.0.

[0083] A molecular weight distribution of 1.0 to 6.0 is preferred because it provides excellent reliability.

[0084] The alkali-soluble resin (B) may be contained in an amount of 5 to 80% by weight, preferably 10 to 70% by weight, and more preferably 10 to 40% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. If the content of the alkali-soluble resin is less than 5% by weight, the sensitivity of the unexposed area to dissolution in a developer may decrease, resulting in the generation of residues. If the content exceeds 80% by weight, the degree of photocuring may decrease, resulting in the exposed area dissolving in a developer.

[0085] [Photopolymerizable compound (C)] In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of a photopolymerization initiator (D) described later, and examples thereof include a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, and a trifunctional or higher polyfunctional photopolymerizable compound.

[0086] Specific examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

[0087] 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, and 3-methylpentanediol di(meth)acrylate.

[0088] Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound 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, and propoxylated dipentaerythritol hexa(meth)acrylate.

[0089] The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

[0090] The photopolymerizable compound may be contained in an amount of 0.5 to 70% by weight, preferably 5 to 50% by weight, relative to 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is contained in the above range, there is no reduction in photosensitivity, the film strength is sufficient, the pattern is not lost during development, the pattern construction is good even in fine pattern portions, and the smoothness of the resist tends to be good, which is preferable.

[0091] [Photopolymerization initiator (D)] In one embodiment of the present invention, the photopolymerization initiator (D) may be any compound capable of polymerizing the photopolymerizable compound (C) without particular limitation. In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, cost, etc., it is preferable to use, as the photopolymerization initiator (D), 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. In particular, acetophenone-based compounds are preferable in terms of pattern characteristics.

[0092] 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.

[0093] 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.

[0094] 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]-

[0033] Examples of the 2,4-bis(trichloromethyl)-6-[2-(furan)-2-yl)ethenyl]-1,3,5-triazine include 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. An example of a commercially available product is TAZ-PP (manufactured by New Japan Chemical Co., Ltd.).

[0095] Specific examples of the biimidazole-based 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 biimidazole compounds in which the phenyl groups at the 4,4',5,5' positions are substituted with carboalkoxy 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.

[0096] Specific examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and commercially available products thereof include CGI-124 (manufactured by Ciba-Geigy), CGI-224 (manufactured by Ciba-Geigy), Irgacure OXE-01 (manufactured by BASF), Irgacure OXE-02 (manufactured by BASF), N-1919 (manufactured by Adeka Corporation), and NCI-831 (manufactured by Adeka Corporation).

[0097] Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0098] Furthermore, the photopolymerization initiator (D) may be used in combination with 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 according to one embodiment of the present invention can further increase the sensitivity and improve productivity.

[0099] The photopolymerization initiation aid (d1) may preferably be, 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.

[0100] Specific examples of the amine compound that can be used 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, with aromatic amine compounds being particularly preferred.

[0101] 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.

[0102] 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).

[0103] The photopolymerization initiator (D) may be contained in an amount of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on 100% by weight of the total solid content of the colored photosensitive resin composition of the present invention. Within this range, the colored photosensitive resin composition becomes highly sensitive and exposure time is shortened, thereby improving productivity and maintaining high resolution. In addition, the strength of pixel portions formed using the composition and the smoothness of the surface of the pixel portions may be improved.

[0104] Furthermore, when the photopolymerization initiation aid (d1) is further used, it is preferable to use it in the same content range as that of the photopolymerization initiator (D). When it is used in the above content range, the sensitivity of the colored photosensitive resin composition can be further improved, and the productivity of a color filter formed using the composition can be improved.

[0105] [Solvent (E)] In one embodiment of the present invention, the solvent may be any solvent used in a typical colored photosensitive resin composition, without any particular limitation, as long as it is effective in dissolving other components contained in the colored photosensitive resin composition of the present invention.

[0106] Specific examples of the solvent (E) 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, propylene glycol monoethyl ... alkylene glycol alkyl ether acetates such as 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.

[0107] Among the above solvents, it is more preferable to use an organic solvent having a boiling point of 100°C to 200°C in terms of coatability and drying properties, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

[0108] The solvents exemplified above may be used alone or in combination of two or more.

[0109] The solvent may be contained in the range of 20 to 95% by weight, preferably 25 to 85% by weight, relative to 100% by weight of the entire colored photosensitive resin composition of the present invention. When the solvent is contained in the range, the effect of improving the coatability when the composition is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet coater is achieved.

[0110] [Additive (F)] The colored photosensitive resin composition of the present invention may be used in combination with additives (F) such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-aggregation agents, if necessary.

[0111] Specific examples of the other polymer compounds 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.

[0112] The curing agent is used to improve deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0113] Specific examples of the epoxy compound in the curing agent 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.

[0114] Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

[0115] The curing agents exemplified above may be used alone or in combination of two or more.

[0116] The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

[0117] The polycarboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Specific examples of the epoxy resin curing agents include ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRIES, LTD.), RIKACID HH (manufactured by New Japan Chemical Co., Ltd.), and MH-700 (manufactured by New Japan Chemical Co., Ltd.).

[0118] The surfactant may be used to further improve the film-forming properties of the colored photosensitive resin composition, and a fluorine-based surfactant, a silicone-based surfactant, or the like may be preferably used. Commercially available examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicones, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 manufactured by GE Toshiba Silicones. Commercially available examples of the fluorine-based surfactant include 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.

[0119] 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-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

[0120] The adhesion promoters exemplified above may be used alone or in combination of two or more.

[0121] Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate.

[0122] Specific examples of the anti-agglomerating agent include, but are not limited to, sodium polyacrylate.

[0123] The colored photosensitive resin composition according to one embodiment of the present invention can be produced, for example, by the following method.

[0124] First, the pigment of the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is approximately 0.2 μm or less. If necessary, a pigment dispersant, part or all of the alkali-soluble resin (B), or a dye may be mixed with the solvent (E) and dissolved or dispersed. The remaining alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the additive (F), as well as the solvent (E) may be added to the mixed dispersion to a predetermined concentration, thereby producing the colored photosensitive resin composition according to the present invention.

[0125] The colored photosensitive resin composition according to the present invention may be used to form a colored pattern. Furthermore, the colored pattern may be used, for example, in a color filter, specifically, a color filter included in an image display device or a solid-state imaging device, as described below.

[0126] Therefore, one embodiment of the present invention relates to a colored pattern and a color filter formed using the above-mentioned colored photosensitive resin composition. The color filter according to one embodiment of the present invention may be manufactured by applying the above-mentioned colored photosensitive resin composition on a substrate, exposing it to light in a predetermined pattern, and developing it to form a colored pattern.

[0127] For example, the colored photosensitive resin composition described above may be applied to a substrate and dried to form a preliminary colored film.

[0128] When the color filter is applied to an image display device, the substrate may be a glass substrate with no coating, or a glass substrate coated with SiNx (protective film) to a thickness of 500 to 1,500 Å.

[0129] 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 a CCD or CMOS) used in the solid-state imaging device, and may include a black matrix or black stripes for isolating each pixel.

[0130] The coating process may include, for example, a coating or printing process such as roll coating, spin coating, slit coating, inkjet printing, and the like.

[0131] The pre-colored film may then be exposed and developed to form a colored pattern corresponding to each pixel.

[0132] The exposure step may include laser exposure using a mask that selectively exposes the pixel regions, followed by selectively removing the unexposed regions with a developer to form the colored pattern.

[0133] The developer may contain, for example, an inorganic or organic alkaline compound. Examples of inorganic alkaline compounds 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 bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia. Examples of organic alkaline compounds include tetramethylammonium hydroxide (TMAH), 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. These compounds may be used alone or in combination of two or more.

[0134] After the development step, a post-baking step may be carried out at, for example, 150 to 230°C.

[0135] One embodiment of the present invention relates to an image display device provided with the above-described color filter.

[0136] The color filter of the present invention can be applied to various image display devices, such as not only conventional liquid crystal display devices (LCDs) but also electroluminescent display devices (ELs), plasma display devices (PDPs), field emission displays (FEDs), and organic light emitting devices (OLEDs).

[0137] The image display device of the present invention includes a configuration known in the art, except that it is provided with the above-described color filters.

[0138] The image display device according to one 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 addition to the color filter described above. In such a case, the light emitted by the light source used in the image display device is not particularly limited, but from the viewpoint of better color reproducibility, a light source emitting blue light may be preferably used.

[0139] An image display device according to one embodiment of the present invention may further include, in addition to the color filter described above, a color filter including only pattern layers of two hues selected from a red pattern layer, a green pattern layer, and a 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 pattern layers of two hues are included, a light source that emits light of a wavelength that represents the remaining hues may be used. For example, when only a red pattern layer and a 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 transparent pattern layer allows the blue light to pass through, resulting in a blue color.

[0140] An embodiment of the present invention relates to a solid-state imaging device provided with the above-described color filter.

[0141] The solid-state imaging device may include, for example, a CMOS Image Sensor (CIS).

[0142] 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.

Example

[0143] 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.

[0144] 〔Synthesis Example 1: Synthesis of alkali-soluble resin (b1-1)〕 A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was prepared. 25.43 g (0.1 mol) of (3-phenoxyphenyl) methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytris[oxy(1-oxohexane-1,6-diyl)], 36.03 g (0.5 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged into the monomer dropping funnel, and then stirred and mixed. A mixture of 6 g of n-dodecanethiol and 24 g of PGMEA was prepared in the chain transfer agent dropping tank and stirred and mixed. Next, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 °C with stirring. Subsequently, the dropping of the monomer and the chain transfer agent was started from each dropping funnel. The dropping was carried out for 2 hours while maintaining 90 °C, the temperature was raised to 1,10 °C after 1 hour and maintained for 3 hours, and then an alkali-soluble resin (b1-1) having an acid value of 50 mgKOH / g in terms of solid content was obtained. At this time, the weight average molecular weight in terms of polystyrene measured by GPC was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85. The GPC measurement conditions are as follows.

[0145] <GPC measurement conditions> Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection) Column temperature: 40℃ Mobile phase solvent: tetrahydrofuran Flow rate: 1.0ml / min Injection amount: 50ul Detector: RI Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran) Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight average molecular weight to the number average molecular weight of the alkali-soluble resin obtained above was taken as the molecular weight distribution (Mw / Mn).

[0146] [Synthesis Example 2: Synthesis of alkali-soluble resin (b1-2)] Alkali-soluble resin (b1-2) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 50.86 g (0.2 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 28.82 g (0.4 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0147] [Synthesis Example 3: Synthesis of alkali-soluble resin (b1-3)] Alkali-soluble resin (b1-3) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 76.28 g (0.3 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 21.62 g (0.3 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 30 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0148] [Synthesis Example 4: Synthesis of alkali-soluble resin (b1-4)] Alkali-soluble resin (b1-4) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 14.41 g (0.2 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 20 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0149] [Synthesis Example 5: Synthesis of alkali-soluble resin (b1-5)] Alkali-soluble resin (b1-5) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 141.6 g (0.3 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 21.62 g (0.3 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 30 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0150] [Synthesis Example 6: Synthesis of alkali-soluble resin (b1-6)] Alkali-soluble resin (b1-6) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 94.40 g (0.2 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 28.82 g (0.4 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0151] [Synthesis Example 7: Synthesis of alkali-soluble resin (b1-7)] Alkali-soluble resin (b1-7) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 47.20 g (0.1 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 36.03 g (0.5 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 50 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0152] Comparative Synthesis Example 1: Synthesis of alkali-soluble resin (b2-1) Except for using 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate and 43.24 g (0.6 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 60 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0153] Comparative Synthesis Example 2: Synthesis of alkali-soluble resin (b2-2) Except for using 127.14 g (0.5 mol) of (3-phenoxyphenyl)methyl acrylate and 36.03 g (0.5 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 50 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0154] Comparative Synthesis Example 3: Synthesis of alkali-soluble resin (b2-3) Except for using 152.57 g (0.6 mol) of (3-phenoxyphenyl)methyl acrylate and 28.82 g (0.4 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0155] Comparative Synthesis Example 4: Synthesis of alkali-soluble resin (b2-4) Synthesis was carried out in the same manner as in Synthesis Example 1, except that 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)] and 43.24 g (0.6 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 60 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0156] Comparative Synthesis Example 5: Synthesis of alkali-soluble resin (b2-5) Except for using 236 g (0.5 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)] and 36.03 g (0.5 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 50 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0157] Comparative Synthesis Example 6: Synthesis of alkali-soluble resin (b2-6) Synthesis was carried out in the same manner as in Synthesis Example 1, except that 283.2 g (0.6 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)] and 28.82 g (0.4 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH / g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw / Mn) of 1.85.

[0158] [Examples 1 to 7 and Comparative Examples 1 to 6: Production of Colored Photosensitive Resin Compositions] Each component was mixed according to the composition shown in Tables 1 and 2 below to prepare a colored photosensitive resin composition (unit: % by weight).

[0159] [Table 1]

[0160] [Table 2]

[0161] Colorant: CI Pigment Blue 15:6 dispersion (pigment content 12.02% by weight, solids content 19.4% by weight) b1-1: Alkali-soluble resin of Synthesis Example 1 (solid content 36.5% by weight) b1-2: Alkali-soluble resin of Synthesis Example 2 (solid content 36.5% by weight) b1-3: Alkali-soluble resin of Synthesis Example 3 (solid content 36.5% by weight) b1-4: Alkali-soluble resin of Synthesis Example 4 (solid content 36.5% by weight) b1-5: Alkali-soluble resin of Synthesis Example 5 (solid content 36.5% by weight) b1-6: Alkali-soluble resin of Synthesis Example 6 (solid content 36.5% by weight) b1-7: Alkali-soluble resin of Synthesis Example 7 (solid content 36.5% by weight) b2-1: Alkali-soluble resin of Comparative Synthesis Example 1 (solid content 36.5% by weight) b2-2: Alkali-soluble resin of Comparative Synthesis Example 2 (solid content: 36.5% by weight) b2-3: Alkali-soluble resin of Comparative Synthesis Example 3 (solid content 36.5% by weight) b2-4: Alkali-soluble resin of Comparative Synthesis Example 4 (solid content 36.5% by weight) b2-5: Alkali-soluble resin of Comparative Synthesis Example 5 (solid content 36.5% by weight) b2-6: Alkali-soluble resin of Comparative Synthesis Example 6 (solid content 36.5% by weight) Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA, manufactured by Sigma-Aldrich) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (IRGACURE 369, manufactured by Ciba Specialty Chemicals) Additive: Leveling agent SH-8400 (Dow Corning Korea Co., Ltd.) Solvent: Propylene glycol monomethyl ether acetate Experimental Example 1: Colored patterns were formed using the colored photosensitive resin compositions prepared in the Examples and Comparative Examples as described below, and the adhesion, linearity, and residue of the colored patterns were measured by the methods described below. The results are shown in Table 3 below.

[0162] <Formation of colored pattern> The colored photosensitive resin compositions of the Examples and Comparative Examples were applied to the surface of a 4-inch silicon wafer by spin coating, and then the substrate was dried in an oven at 100°C for 90 seconds to volatilize the liquid components and form a thin film. After cooling to room temperature, the formed thin film was exposed using a pattern mask and an i-line stepper (manufactured by Canon Corporation). The silicon wafer substrate with the exposed coating film formed thereon was developed in a 0.2 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), washed with water, and then heated at 220°C for 180 seconds to form a colored pattern. The resulting pattern had a thickness of 1 μm.

[0163] (1) Adhesion measurement The obtained colored pattern was analyzed with a VHX-7000 (manufactured by KEYENCE Corporation) optical microscope to measure the minimum pattern size that could be formed without pattern loss.

[0164] (2) Evaluation of pattern characteristics The obtained colored pattern was analyzed with a VHX-7000 (manufactured by KEYENCE Corporation) optical microscope, and the pattern characteristics (straightness and residue) were evaluated as follows.

[0165] <Straight-line stability evaluation criteria> 5: All four side walls of the pattern are straight 4: The side walls of the four patterns are substantially straight, but include some protrusions 3: Some of the side walls of the four patterns are substantially uneven 2: All four sidewalls of the pattern are substantially uneven 1: No consistent pattern shape formed.

[0166] <Residue evaluation criteria> 5: No residue observed between colored patterns 4: Residue is present in the area between the colored patterns, exceeding 0% and less than 10% of the total area 3: Residue is present in the area between the colored patterns, covering 10% to less than 20% of the total area. 2: Residue is present in 20% to 30% of the total area between the colored patterns 1: Residue is distributed over 30% or more of the total area between the colored patterns.

[0167] Experimental Example 2: The pigment dispersibility of the colored photosensitive resin composition was measured by the following method, and the results are shown in Table 3 below.

[0168] (1) Pigment dispersibility (stability over time) The viscosity of each of the colored photosensitive resin compositions of the Examples and Comparative Examples immediately after production and after standing at 40°C for 7 days was measured at 25°C using a Brookfield Viscometer (Brookfield Viscometer DV-I+, manufactured by BROOKFIELD Corporation), and the difference from the initial viscosity was compared.

[0169] <Evaluation criteria> ◎: Viscosity difference 1% or less ○: Viscosity difference more than 1% but less than 2% △: Viscosity difference more than 2% but less than 5% ×: Viscosity difference over 5%

[0170] [Table 3]

[0171] As shown in Table 3 above, the colored photosensitive resin compositions of Examples 1 to 7, which contained, as alkali-soluble resins, first repeating units containing phenoxybenzyl groups of specific structures and second repeating units containing caprolactone-modified hydroxyalkyl groups, were confirmed to have excellent pigment dispersibility, and also to have excellent adhesion and linearity during the formation of colored patterns, leaving almost no residue.

[0172] In contrast, it was confirmed that the colored photosensitive resin compositions of Comparative Examples 1 to 6, which used alkali-soluble resins that did not contain any of the repeating units with the above-mentioned specific structures, had poor pigment dispersibility, poor pattern adhesion and linearity, and generated residues.

[0173] Although specific aspects of the present invention have been described in detail above, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments and are not intended to limit the scope of the present invention. Those skilled in the art will be able to make various applications and modifications within the scope of the present invention based on the above content.

[0174] Therefore, the true scope of the invention is to be defined by the following claims and their equivalents.

Claims

1. A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, The alkali-soluble resin comprises a first repeating unit represented by the following chemical formula 1 and a second repeating unit represented by the following chemical formula 2: 【Chemistry 1】 In the above formula, R １ ~R ９ is hydrogen, R １０ is hydrogen or a methyl group, R １１ is hydrogen or a methyl group, R １２ is C １ -C3 alkylene group, R １３ is C ３ -C5 alkylene group, n is an integer from 1 to 5.

2. 2. The colored photosensitive resin composition according to claim 1, wherein the first repeating unit represented by Chemical Formula 1 is contained in an amount of 10 to 80 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

3. 2. The colored photosensitive resin composition according to claim 1, wherein the second repeating unit represented by Chemical Formula 2 is contained in an amount of 10 to 70 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

4. A colored pattern formed using the colored photosensitive resin composition according to any one of claims 1 to 3.

5. A color filter comprising the colored pattern according to claim 4 .

6. An image display device comprising the color filter according to claim 5.

7. A solid-state imaging device comprising the color filter according to claim 5.

8. 8. The solid-state imaging device of claim 7, comprising a CMOS Image Sensor (CIS).

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