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. More specifically, the present invention relates to a colored photosensitive resin composition that is excellent in developability and adhesion, can improve pigment dispersibility, and enables formation of a high-resolution and delicate pattern, a color filter formed using the same, and an image display device including the color filter.

Background Art

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

[0003] In recent years, as the number of pixels of color filters used in this type of image sensor has increased, the content of pigments in the colored photosensitive resin composition has been increasing. For this reason, there are problems in that the degree of curing of the colored photosensitive resin composition decreases, it is difficult to ensure pattern characteristics, and residues are generated.

[0004] Therefore, there has been a demand for the development of a colored photosensitive resin composition that is excellent in pattern characteristics such as residue or residual film characteristics and straightness, as well as developability and adhesion, so that high dispersibility of pigments and fine patterning are possible.

[0005] Korean Patent Laid-Open No. 10-2009-0072754 discloses a composition for a color filter containing a pigment and a binder resin, but it is not suitable for application to a color filter for a high-resolution solid-state imaging device described above.

Summary of the Invention

Problems to be Solved by the Invention

[0006] One object of the present invention is to provide a colored photosensitive resin composition that is excellent in developability and adhesion, can improve pigment dispersibility, and enables the formation of a high-resolution and delicate pattern.

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

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

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

[0010] Still further, an object of the present invention is to provide a solid-state imaging device including the color filter.

Means for Solving the Problems

[0011] On the other hand, the present invention provides a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin contains a first repeating unit represented by the following Chemical Formula 1 and a second repeating unit represented by the following Chemical Formula 2.

[0012]

Chem.

[0013] In the above formula, R 1 ~R 9 are each independently hydrogen, halogen, an alkyl group of C 1 -C 10 or an alkoxy group of C 1 -C 10 , and R 10is a hydrogen or methyl group, R 11 is a hydrogen or methyl group, R 12 is C 1 -C 10 is an alkylene group of R 13 is C 3 -C 7 is an alkylene group of n is an integer from 1 to 20.

[0014] In one embodiment of the present invention, R 1 ~R 9 are hydrogen, R 12 is C 1 -C 3 is an alkylene group of R 13 is C 3 -C 5 is an alkylene group of n may be an integer from 1 to 5.

[0015] In one embodiment of the present invention, the first repeating unit represented by Chemical Formula 1 may be included in the range of 10 to 80 mol% with respect to 100 mol% of the total 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 included in the range of 10 to 70 mol% with respect to 100 mol% of the total 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 characterized in that the color filter is provided.

[0020] On the other hand, the present invention provides a solid-state imaging device characterized by including the color filter.

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

Advantages of the Invention

[0022] The colored photosensitive resin composition according to the present invention contains an alkali-soluble resin containing a first repeating unit containing a phenoxybenzyl group having a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group, so that it has excellent developability with TMAH (tetramethyl ammonium hydroxide) and has no residue when forming a colored pattern. In addition, it has excellent adhesion, pattern straightness, and can improve the dispersibility of the pigment.

Embodiments for Carrying Out the Invention

[0023] Hereinafter, the present invention will be described in more detail.

[0024] One embodiment of the present invention is a colored photosensitive resin composition containing 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) contains a first repeating unit containing a phenoxybenzyl group having a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group. The present invention relates to a colored photosensitive resin composition.

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

[0026] 〔Colorant (A)〕 In one embodiment of the present invention, the colorant (A) may be an organic pigment, an inorganic pigment, or a dye generally used in the art.

[0027] The organic pigment may be any of various pigments used in printing inks, inkjet inks, etc. Specifically, phthalocyanine, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, or diketopyrrolopyrrole pigments, etc. may be mentioned.

[0028] As for the pigment, if necessary, surface treatment using resin treatment, pigment derivatives into which acidic groups or basic groups have been introduced, graft treatment on the pigment surface with a polymer compound, etc., micronization treatment by a sulfuric acid micronization method, etc., or cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, etc. may be performed.

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

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

[0031] In particular, as the pigment, specifically, compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists) may be used. More specifically, pigments with the following Color Index (C.I.) numbers may be used, but it is not necessarily limited to these.

[0032] C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, and 242 C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71 C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264, and 277 C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38 C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76 C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62, and 63 C.I. Pigment Brown 28 C.I. Pigment Black 1 and 7, etc. Among the exemplified C.I. pigment pigments, preferably, a pigment selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36 or C.I. Pigment Green 58 may be used.

[0033] It is preferable to use a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of adding a pigment dispersant and performing a dispersion treatment can be mentioned. According to this method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

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

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

[0036] The pigment dispersant is usually used in an amount of 1 part by weight or less, preferably in the range of 0.05 to 0.5 part by weight, based on 1 part by weight of the pigment. When the pigment dispersant is used in such a content, it is preferable because a pigment with a uniformly dispersed particle size can be obtained.

[0037] The dye may be used without particular limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance may be used.

[0038] As the dye, those selected from acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamide forms of acidic dyes, etc. and their derivatives may be used. In addition, azo-based, xanthene-based, phthalocyanine-based acidic dyes and their derivatives can also be selected.

[0039] Preferably, the dye includes compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in the Dyeing Notes (Color Dyeing Company).

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

[0041] Also, as C.I. Acid Dyes, Yellow dyes such as C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; Red dyes such as C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; Blue dyes such as C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19; Examples of green dyes include C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.

[0042] Also, as C.I. direct dyes, Yellow dyes such as C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc.; Red dyes such as C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, etc.; Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc.; Blue dyes such as C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc.; Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc.; Examples of green dyes include C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.

[0043] Also, as C.I. mordant dyes, yellow dyes such as C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc.; red dyes such as C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, etc.; orange dyes such as C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.; blue dyes such as C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc.; violet dyes such as C.I. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc.; green dyes such as C.I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are included.

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

[0045] The coloring agent (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 coloring agent (A) is within the above range, there are advantages that the color density of the pixel becomes sufficient during film formation, and the drop-out property of the non-pixel portion does not decrease and no residue is generated during development.

[0046] In the present invention, the solid content in the colored photosensitive resin composition means the sum of the components obtained by removing the solvent.

[0047] 〔Alkali-soluble resin (B)〕 In one embodiment of the present invention, the alkali-soluble resin (B) usually has reactivity and alkali solubility by the action of light or heat, 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]

Chemical formula

[0050] In the above formula, R 1 ~R 9 are each independently hydrogen, halogen, an alkyl group of C 1 -C 10 , or an alkoxy group of C 1 -C 10 , R 10 is hydrogen or a methyl group, R 11 is hydrogen or a methyl group, R 12 is an alkylene group of C 1 -C 10 , R 13 is an alkylene group of C 3 -C 7 , n is an integer of 1 to 20.

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

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

[0053] As used herein, C 1 -C 10 The alkylene group means a linear or branched divalent hydrocarbon having 1 to 10 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, pentylene, etc., but is not limited thereto.

[0054] As used herein, C 3 -C 7 The alkylene group means a linear or branched divalent hydrocarbon having 3 to 7 carbon atoms, and includes, for example, propylene, butylene, pentylene, hexylene, etc., but is not limited thereto.

[0055] In one embodiment of the present invention, R 1 ~R 9 is hydrogen, R 12 is an alkylene group of C 1 -C 3 and R 13 is an alkylene group of C 3 -C 5 and n may be an integer from 1 to 5.

[0056] The first repeating unit represented by the chemical formula 1 may be introduced using a compound represented by the following chemical formula 3.

[0057]

Chem.

[0058] In the above formula, R 1 ~R 10 are as defined in the chemical formula 1.

[0059] By the alkali-soluble resin (B) containing the first repeating unit represented by the chemical formula 1, high-resolution characteristics, fine patterning characteristics, etc. can be improved. For example, in the first repeating unit, two benzene ring units can be rotatably bonded by an ether bond. Due to the characteristics of such a bonding structure, the unexposed portion can be cleanly removed by the developing solution in the unexposed area of the substrate. Therefore, in the unexposed area between the exposed portions with a fine pitch, a colored pattern that is clean and has excellent straightness can be obtained without generating residues.

[0060] The second repeating unit represented by the chemical formula 2 may be introduced using a compound represented by the following chemical formula 4.

[0061]

Chem.

[0062] In the above formula, R 11 ~R 13 and n are as defined in the chemical formula 2.

[0063] By the alkali-soluble resin (B) containing the second repeating unit represented by the chemical formula 2, the adhesion and developability can be improved, and the straightness 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 repeating unit may be derived from the carboxylic acid monomer and a reactive monomer capable of bonding or copolymerizing with the carboxylic acid monomer.

[0067] Examples of the reactive monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; unsaturated carboxylate compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl (meth)acrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; and 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. 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 binding to the carboxylic acid monomer, the third repeating unit may be derived from the carboxylic acid monomer and the unsaturated glycidyl carboxylate compound, or from the carboxylic acid monomer, the unsaturated glycidyl carboxylate compound, and an acid anhydride capable of binding to the unsaturated glycidyl carboxylate compound.

[0069] The acid anhydrides used herein include, but are not limited to, 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 anhydride, hexahydrophthalic anhydride, carbic anhydride, etc. From the perspective of easy 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 particularly, 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 a repeating unit derived from (meth)acrylic acid and glycidyl (meth)acrylate, or may include a repeating unit derived from (meth)acrylic acid, glycidyl (meth)acrylate, and succinic anhydride. For example, the third repeating unit may include units respectively derived from (meth)acrylic acid and glycidyl (meth)acrylate, 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 can also improve the adhesion of the composition or the 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 repeatedly arranged in a constant manner, or may be a random copolymer in which these are repeatedly arranged randomly.

[0073] In one embodiment of the present invention, the first repeating unit may be included in the range of 10 to 80 mol%, preferably 20 to 40 mol%, based on 100 mol% of the total repeating units constituting the alkali-soluble resin.

[0074] In one embodiment of the present invention, the second repeating unit may be included in the range of 10 to 70 mol%, preferably 20 to 40 mol%, based on 100 mol% of the total repeating units constituting the alkali-soluble resin.

[0075] In one embodiment of the present invention, the third repeating unit may be included in the range of 10 to 70 mol%, preferably 20 to 50 mol%, based on 100 mol% of the total repeating units constituting the alkali-soluble resin.

[0076] When the first repeating unit and the second repeating unit are each included within the range of the mol%, developability, adhesion, and pigment dispersibility can be improved, and high-resolution and delicate pattern formation is possible.

[0077] Furthermore, when the third repeating unit is included within the range of the mol%, 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 the polymer, and can usually be determined by titration using an aqueous potassium hydroxide solution.

[0079] The polystyrene-reduced weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluent solvent) of the alkali-soluble resin 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 ranges of the acid value, weight average molecular weight, and double bond equivalent, developability, pattern characteristics, and pigment dispersibility 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 preferable because of 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, more preferably 10 to 40% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is less than 5% by weight, the sensitivity of the unexposed portion to be dissolved in the developer may decrease and residues may occur. When it exceeds 80% by weight, the degree of photocuring may decrease and the exposed portion may be dissolved in the 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 monofunctional photopolymerizable compounds, bifunctional photopolymerizable compounds, and polyfunctional photopolymerizable compounds having three or more functional groups.

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

[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, 3-methylpentanediol di(meth)acrylate, and the like.

[0088] Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, and the like.

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

[0090] The photopolymerizable compound may be contained in the range of 0.5 to 70% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is contained within the above range, there is no reduction in photosensitivity, the strength of the film is sufficient, there is no disappearance of the pattern during development, the pattern formation is good even in the fine pattern portion, 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 used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., the photopolymerization initiator (D) is preferably 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, and particularly 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, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

[0093] Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

[0094] Specific examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran)-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan)-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Commercially available products include TAZ-PP (manufactured by Shin Nippon Rika Co., Ltd.).

[0095] Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which the phenyl groups at the 4,4',5,5' positions are substituted with carboxyalkoxy groups, etc. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably used.

[0096] Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxyoxime), etc. Commercially available products 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), NCI-831 (manufactured by Adeka), etc.

[0097] Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0098] In addition, the photopolymerization initiator (D) may be used in combination with a photopolymerization initiator aid (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to an embodiment of the present invention can improve productivity by further increasing the sensitivity by containing the photopolymerization initiator aid (d1).

[0099] As the photopolymerization initiator aid (d1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group may be preferably used.

[0100] As the amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, 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 may be used, and it is particularly preferable to use an aromatic amine compound.

[0101] The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. may be mentioned.

[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), tetraethylene glycol bis(3-mercaptopropionate), etc.

[0103] The photoinitiator (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 in the colored photosensitive resin composition of the present invention. Within the above range, the colored photosensitive resin composition has higher sensitivity, the exposure time is shortened, so the productivity is improved, and a high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion may be improved.

[0104] Further, when the photoinitiator assistant (d1) is further used, it is preferable to use the same content range as that of the photoinitiator (D). When used within the content range, the sensitivity of the colored photosensitive resin composition is further improved, and the productivity of the color filter formed using the composition can be improved.

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

[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; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

[0107] Among these solvents, it is more preferable to use an organic solvent having a boiling point of 100°C to 200°C from the viewpoints of coatability and drying property. 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 exemplified solvents may be used alone or in admixture of two or more thereof.

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

[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, as 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 enhance deep curing and mechanical strength. 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-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester-based resins, glycidyl amine-based resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxidized products, isoprene (co)polymer epoxidized products, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, and the like.

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

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

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

[0117] As the polycarboxylic acid anhydrides, those commercially available as epoxy resin hardeners may be used. Specific examples of the epoxy resin hardeners include, for example, Adeka Hardener EH-700 (manufactured by Adeka Corporation), Rica Sid HH (manufactured by Shin Nippon Rika Co., Ltd.), MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), and the like.

[0118] The surfactant may be used to further improve the film-forming property of the colored photosensitive resin composition, and fluorine-based surfactants, silicone-based surfactants, and the like may be preferably used. Examples of the silicone-based surfactants include, as commercial products, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. manufactured by Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. manufactured by GE Toshiba Silicone Co., Ltd. Examples of the fluorine-based surfactants include, as commercial products, Megafac F-470, F-471, F-475, F-482, F-489, etc. 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-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like.

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

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

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

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

[0124] First, a pigment among the colorant (A) is mixed with a solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. At this time, if necessary, a pigment dispersant, a part or all of the alkali-soluble resin (B), or a dye may be mixed and dissolved or dispersed together with the solvent (E). To the mixed dispersion, the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the additive (F), and if necessary, the solvent (E) are further added to a predetermined concentration to produce the colored photosensitive resin composition according to the present invention.

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

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

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

[0128] When the color filter is applied to an image display device, the substrate may be a glass substrate without any coating, or a glass substrate coated with SiNx (protective film) having 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 (for example, a silicon substrate for CCD or CMOS) utilized in the solid-state imaging device. The substrate may also include a black matrix or black stripe for isolating each pixel.

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

[0131] Next, the preliminary colored film may 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. Next, the colored pattern may be formed by selectively removing the non-exposed regions with a developer.

[0133] The developer may include, for example, an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, and the like. Examples of the organic alkaline compound include tetramethylammonium hydroxide (TMAH), 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These may be used alone or in combination of two or more.

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

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

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

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

[0138] The image display device according to an embodiment of the present invention may further include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filter described above. In such a case, the emitted light of the light source applied to the image display device is not particularly limited, but from the aspect of better color reproducibility, a light source that emits blue light may preferably be used.

[0139] The image display device according to an embodiment of the present invention may further include a color filter including only two kinds of hue pattern layers among the red pattern layer, the green pattern layer, and the blue pattern layer in addition to the color filter described above. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only two kinds of hue pattern layers are provided, a light source that emits light having a wavelength indicating the remaining hue that is not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source that emits blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the blue light passes through the transparent pattern layer to show blue.

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

[0141] The solid-state imaging device may include, for example, a complementary metal-oxide-semiconductor image sensor (CMOS Image Senser: 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 by way of examples, comparative examples, and experimental examples. It should be noted that these examples, comparative examples, and experimental examples are for illustrative purposes only, 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-hydroxytri[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 110° 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-GEL G4000HXL + TSK-GEL G2000HXL (serial connection) Column temperature: 40 °C Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50 μl Detector: RI Measured sample concentration: 0.6 mass% (solvent = tetrahydrofuran) Calibration standard substance: 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 and the number average molecular weight of the alkali-soluble resin obtained above was defined 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 performing 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 acid value of the thus synthesized alkali-soluble resin was 40 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85.

[0147] 〔Synthesis Example 3: Synthesis of alkali-soluble resin (b1-3)〕 Alkali-soluble resin (b1-3) was obtained by performing 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 acid value of the thus synthesized alkali-soluble resin was 30 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85.

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

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

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

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

[0152] 〔Comparative Synthesis Example 1: Synthesis of Alkali-Soluble Resin (b2-1)〕 (3-Phenoxyphenyl)methyl acrylate 101.71 g (0.4 mol) and acrylic acid 43.24 g (0.6 mol) were used, and synthesis was carried out in the same manner as in Synthesis Example 1 above. The acid value of the thus synthesized alkali-soluble resin was 60 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85.

[0153] 〔Comparative Synthesis Example 2: Synthesis of Alkali-Soluble Resin (b2-2)〕 (3-Phenoxyphenyl)methyl acrylate 127.14 g (0.5 mol) and acrylic acid 36.03 g (0.5 mol) were used, and synthesis was carried out in the same manner as in Synthesis Example 1 above. The acid value of the thus synthesized alkali-soluble resin was 50 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85.

[0154] 〔Comparative Synthesis Example 3: Synthesis of Alkali-Soluble Resin (b2-3)〕 (3-Phenoxyphenyl)methyl acrylate 152.57 g (0.6 mol) and acrylic acid 28.82 g (0.4 mol) were used, and synthesis was carried out in the same manner as in Synthesis Example 1 above. The acid value of the thus synthesized alkali-soluble resin was 40 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 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 acid value of the thus synthesized alkali-soluble resin was 60 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85.

[0156] [Comparative Synthesis Example 5: Synthesis of Alkali-Soluble Resin (b2-5)] Synthesis was carried out in the same manner as in Synthesis Example 1, except that 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 were used. The acid value of the thus synthesized alkali-soluble resin was 50 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 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 acid value of the thus synthesized alkali-soluble resin was 40 mgKOH / g, the weight average molecular weight was 10,000, and the molecular weight distribution (Mw / Mn) was 1.85.

[0158] [Examples 1 to 7 and Comparative Examples 1 to 6: Production of Colored Photosensitive Resin Compositions] Colored photosensitive resin compositions were produced by mixing the respective components in the compositions shown in Tables 1 and 2 below (unit: wt%).

[0159] [Table 1]

[0160]

Table 2

[0161] Colorant: C.I. Pigment Blue 15:6 dispersion (pigment content 12.02 wt%, solid content 19.4 wt%) b1-1: Alkali-soluble resin of Synthesis Example 1 (solid content 36.5 wt%) b1-2: Alkali-soluble resin of Synthesis Example 2 (solid content 36.5 wt%) b1-3: Alkali-soluble resin of Synthesis Example 3 (solid content 36.5 wt%) b1-4: Alkali-soluble resin of Synthesis Example 4 (solid content 36.5 wt%) b1-5: Alkali-soluble resin of Synthesis Example 5 (solid content 36.5 wt%) b1-6: Alkali-soluble resin of Synthesis Example 6 (solid content 36.5 wt%) b1-7: Alkali-soluble resin of Synthesis Example 7 (solid content 36.5 wt%) b2-1: Alkali-soluble resin of Comparative Synthesis Example 1 (solid content 36.5 wt%) b2-2: Alkali-soluble resin of Comparative Synthesis Example 2 (solid content 36.5 wt%) b2-3: Alkali-soluble resin of Comparative Synthesis Example 3 (solid content 36.5 wt%) b2-4: Alkali-soluble resin of Comparative Synthesis Example 4 (solid content 36.5 wt%) b2-5: Alkali-soluble resin of Comparative Synthesis Example 5 (solid content 36.5 wt%) b2-6: Alkali-soluble resin of Comparative Synthesis Example 6 (solid content 36.5 wt%) 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: Levelling agent SH-8400 (manufactured by Dow Corning Korea Co., Ltd.) Solvent: Propylene Glycol Monomethyl Ether Acetate Experimental Example 1: Using the colored photosensitive resin compositions produced in the above Examples and Comparative Examples, a colored pattern was formed as follows. After measuring the adhesion, straightness, and residue of the colored pattern by the following methods, the results are shown in Table 3 below.

[0162] <Formation of Colored Pattern> The colored photosensitive resin compositions of the above Examples and Comparative Examples were applied onto 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 thin film formed using a pattern mask and an i-line stepper (manufactured by CANON) was exposed. The silicon wafer substrate on which the exposed coating film was formed was developed with 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 thickness of the obtained pattern was 1 μm.

[0163] (1) Measurement of Adhesion The obtained colored pattern was analyzed with a VHX-7000 (manufactured by KEYENCE) optical microscope to measure the size of the smallest pattern 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) optical microscope to evaluate the pattern characteristics (straightness and residue) as follows.

[0165] <Evaluation Criteria for Straightness> 5: All four side walls of the pattern are linear 4: All four side walls of the pattern contain some protrusions but are substantially linear 3: Some of the four side walls of the pattern are substantially uneven 2: All four side walls of the pattern are substantially uneven 1: No formation of a certain pattern shape.

[0166] <Evaluation Criteria for Residues> 5: No residue observed between coloring patterns 4: Residue distribution exists with the overall area ratio between coloring patterns being over 0% and less than 10% 3: Residue distribution exists with the overall area ratio between coloring patterns being 10% or more and less than 20% 2: Residue distribution exists with the overall area ratio between coloring patterns being 20% or more and less than 30% 1: Residue distribution exists with the overall area ratio between coloring patterns being 30% or more.

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

[0168] (1) Pigment Dispersibility (Stability over Time) The viscosities of the colored photosensitive resin compositions of the above Examples and Comparative Examples immediately after production and after standing at 40 °C for 7 days were measured at 25 °C using a Brookfield Viscometer (DV-I +, manufactured by BROOKFIELD), and the differences from the initial viscosities were compared.

[0169] <Evaluation Criteria> ◎: Viscosity difference is 1% or less ○: Viscosity difference is over 1% and 2% or less △: Viscosity difference is over 2% and 5% or less ×: Viscosity difference is over 5%

[0170]

Table 3

[0171] As shown in Table 3 above, the colored photosensitive resin compositions of Examples 1 to 7 containing the first repeating unit containing a phenoxybenzyl group with a specific structure and the second repeating unit containing a caprolactone-modified hydroxyalkyl group as the alkali-soluble resin were confirmed to be excellent in pigment dispersibility, and excellent in adhesion and straightness during the formation of coloring patterns, with almost no residue.

[0172] On the other hand, it was confirmed that the colored photosensitive resin compositions of Comparative Examples 1 to 6 using an alkali-soluble resin not containing any of the repeating units having the specific structure described above had poor pigment dispersibility, poor adhesion and straightness of the pattern, and generation of residues.

[0173] As described above, the specific part of the present invention has been described in detail. However, it is obvious to those having ordinary knowledge in the technical field to which the present invention pertains that such specific description is merely a preferred embodiment, and the scope of the present invention is not limited thereby. Those having ordinary knowledge in the technical field to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above content.

[0174] Therefore, it can be said that the substantial scope of the present invention is defined by the claims and their equivalents.

Claims

1. A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a 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 are each independently hydrogen, halogen, or C １ -C １０ or an alkyl group of C １ -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 C １ -C １０ is an alkylene group of the formula: R １３ is C ３ -C ７ is an alkylene group of the formula: n is an integer from 1 to 20.

2. R １ ~R ９ is hydrogen, R １２ is C １ -C ３ is an alkylene group of the formula: R １３ is C ３ -C ５ is an alkylene group of the formula:

2. The colored photosensitive resin composition according to claim 1, wherein n is an integer of 1 to 5.

3. 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.

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

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

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

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

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

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

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