Colored photosensitive composition, color filter, and image display device including the same

Abstract

The present invention provides a colored photosensitive composition, a color filter, and an image display device. The colored photosensitive composition comprises a colorant and an additive having a predetermined structure. The colorant comprises a dye, and the content of the dye is 80% by weight or greater relative to the total weight of the colorant. The present invention can provide a colored photosensitive composition having high contrast and brightness.

Description

Technical Field

[0001] The present invention relates to a colored photosensitive composition, a color filter, and an image display device including the same. More specifically, it relates to a colored photosensitive composition containing a colorant and an additive, a color filter, and an image display device including the same. Background Art

[0002] Color filters are optical elements widely used in imaging elements, liquid crystal display elements, and the like. Color filters can be built into liquid crystal display devices to color images, or built into imaging elements to obtain color images. The manufacturing process of the color filter begins with uniformly coating a photosensitive composition containing a colorant on a substrate on which a black matrix pattern is formed. Specifically, in order to form pixels of each color on the color filter, the following steps are implemented: a pre-baking step of heating and drying the applied photosensitive composition to form a coating film; an exposure step of selectively irradiating the coating film with ultraviolet rays using a mask; and a development step of dissolving the uncured portion using a developer. In addition, a post-baking step of heating the pixels that have undergone the development step can be added as needed.

[0003] Colored photosensitive compositions, as photosensitive compositions containing colorants, can be used as materials for forming colored patterns. In order to reduce the power consumption required when driving image display devices, it is required to develop color filters with higher brightness. In addition, as image display devices are becoming lighter and thinner, colored photosensitive compositions are required to provide high brightness, high tinting power, and high contrast (High contrast ratio) characteristics. Therefore, the use of pigments as colorants continues to increase. However, if the concentration of the pigment becomes higher, the storage stability and even the coating properties of the colored photosensitive compositions may be reduced. In addition, due to a decrease in formability, it may be difficult to produce a color filter with sufficient performance.

[0004] Patent Document 1 relates to a colored composition comprising a colorant and a polymerizable compound, disclosing a polymer in which the colorant has a site that emits fluorescence and a site that absorbs the corresponding fluorescence. Patent Document 1 claims that the colored composition exhibits high contrast and excellent heat resistance. However, the composition in Patent Document 1 has limitations in terms of storage stability and coating properties due to the high pigment concentration.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Korean Patent Publication No. 10-2015-0101934 Summary of the Invention

[0008] Issues to be addressed

[0009] An object of the present invention is to provide a colored photosensitive composition having improved color characteristics and optical characteristics.

[0010] An object of the present invention is to provide a color filter formed from the above-mentioned colored photosensitive composition and having color characteristics and optical characteristics with improved reliability.

[0011] An object of the present invention is to provide an image display device including the above-mentioned color filter.

[0012] Solutions to Problems

[0013] 1. A colored photosensitive composition comprising a colorant containing a dye and an additive represented by the following Chemical Formula 1, wherein the content of the dye is 80% by weight or more relative to the total weight of the colorant:

[0014] [Chemical Formula 1]

[0015] (X + ) n (Y) m-

[0016] (In the above Chemical Formula 1, X includes a heterocyclic ring, and Y includes one or more elements selected from the group consisting of tungsten (W), molybdenum (Mo), silicon (Si), germanium (Ge), arsenic (As), and phosphorus (P), and an oxygen atom).

[0017] 2. The colored photosensitive composition according to 1 above, wherein the colorant does not contain a pigment.

[0018] 3. The colored photosensitive composition according to 1 above, wherein the heterocycle of Chemical Formula 1 contains a cationic atom having a formal charge of +1, and the cationic atom is any one of nitrogen, carbon, sulfur, and phosphorus.

[0019] 4. The colored photosensitive composition according to item 3 above, wherein the cationic atom is bonded with one or more functional groups selected from the group consisting of hydrogen, a C1-C10 linear alkyl group, a C3-C10 branched alkyl group, a halogen group, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, a hydroxyl group, a formyl group, an ester group, a carboxyl group, and an amino group.

[0020] 5. The colored photosensitive composition according to the above 4, wherein the heterocyclic ring contains an unsaturated ring having 5 to 7 ring atoms.

[0021] 6. The colored photosensitive composition according to 5 above, wherein the heterocyclic ring includes a bicyclic structure.

[0022] 7. The colored photosensitive composition according to 5 above, wherein the heterocyclic ring has any one of the structures of pyrazine, pyridine, pyridazine, pyrimidine, pyrrole and imidazole, the cationic atom is nitrogen, and the cationic atom is bonded to a C1-C10 linear or C3-C10 branched alkyl group.

[0023] 8. The colored photosensitive composition according to 7 above, wherein the cationic atom is bonded to a C1-C6 linear alkyl group.

[0024] 9. The colored photosensitive composition according to item 1 above, wherein Y is a tungsten-containing heteropoly acid or isopoly acid.

[0025] 10. The colored photosensitive composition according to 9 above, wherein the ratio of the content of the colorant to the content of the additive is 5 to 20.

[0026] 11. A color filter comprising a colored layer formed from the colored photosensitive composition according to 1 above.

[0027] 12. An image display device comprising the color filter according to 11 above.

[0028] Effects of the Invention

[0029] The colored photosensitive composition according to an embodiment of the present invention includes a colorant including a dye and an additive. The content of the dye may be 80% by weight or more relative to the total weight of the colorant.

[0030] Furthermore, the colorant does not need to contain a pigment. Therefore, a colored photosensitive composition with high contrast and brightness can be provided.

[0031] The colored photosensitive composition of the exemplary embodiment includes an additive that is compatible with the dye (ie, colorant) and can improve the reliability of the colored photosensitive composition. The additive can effectively absorb light energy to improve the heat resistance and light resistance of the colored photosensitive composition.

[0032] In an exemplary embodiment, the additive may include a heterocyclic cation and a polyacid anion. In addition, the heterocyclic cation may be an unsaturated heterocyclic cation containing a nitrogen atom, and the polyacid anion may be a heteropolyacid anion or an isopolyacid anion containing a tungsten atom. For example, a pyridine containing a C1-C10 straight-chain alkyl group or a C3-C10 branched-chain alkyl group may be used. The cationic additive can further improve the light resistance of the colored photosensitive composition and the life of the color filter. DETAILED DESCRIPTION

[0033] The present specification discloses a colored photosensitive composition comprising a colorant and an additive represented by the following Chemical Formula 1. The colorant comprises a dye, and the content of the dye is 80% by weight or more relative to the total weight of the colorant.

[0034] [Chemical Formula 1]

[0035] (X + ) n (Y) m-

[0036] In the above Chemical Formula 1, X includes a heterocyclic ring, and Y includes one or more elements selected from the group consisting of tungsten, molybdenum, silicon, germanium, arsenic, and phosphorus, and an oxygen atom.

[0037] <Colorant>

[0038] In exemplary embodiments, the colorant comprises a dye.

[0039] Dyes are organic or inorganic compounds that dissolve in a solvent and exhibit color in the ultraviolet, visible, and infrared regions. Non-limiting examples of dye precursors include nitro, nitroso, xanthene, triarylmethane, cyanine, pyran, squarilium, coumarin, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODYPY), perylene, fluororesin, anthraquinone, anthracene, azo, quinophthaline, indoline, pyrrolopyrrole, quinoneimine, pyrazole, quinoline, azomethine, stilbene, acridine, azine, Compounds such as oxazine, naphthamide, benzoquinone, naphthioquinone, porphyrin, phthalocyanine, naphthalocyanine, indigo, diimonium, naphthol, metal complexes and derivatives thereof are also included, but are not limited thereto.

[0040] As dyes included in the colorant, compounds classified as solvent, acid, basic, reactive, direct, disperse, or vat in the Colour Index (published by The Society of Dyers and Colourists) can be used.

[0041] As specific examples of dyes, there are CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reaction Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI Disperse Yellow 54, 76; CI Solvent Orange 41, 54, 56, 99; CI Acid Orange 56, 74, 95, 108, 149, 162; CI Reaction Yellow 54 ... Orange 16; CI Direct Orange 26; CI Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 102; CI Solvent Green 1, 5; CI Acid Green 3, 5, 9, 25, 28; CI Basic Green 1; CI Vat Green 1, etc.

[0042] In exemplary embodiments, dyes can be used in combination with additives to simultaneously improve the heat resistance and light resistance of the colored photosensitive composition. Furthermore, to achieve high brightness, the dye content is preferably 80% by weight or greater, more preferably 90% or greater, and most preferably 99% or greater, relative to the total weight of the colorant. Using only a dye as a colorant can further improve both heat resistance and light resistance.

[0043] As pigments, known pigments can be used. For example, it is contemplated that pigments classified as pigments in the Color Index (published by the Society of Dyers and Colourists) can be used. However, in order to achieve high brightness, the content of the pigment is preferably less than 20% by weight, more preferably less than 5% by weight, and most preferably less than 1% by weight relative to the overall weight of the colorant.

[0044] In exemplary embodiments, additives and colorants containing dyes may be used together to improve light resistance. Even if the colorant does not contain a pigment, heat resistance and light resistance of the colored photosensitive composition can be improved by using the additives together.

[0045] Examples of pigments include CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and 269; CI Pigment Blue 15, 15:3, 15:4, 15:6, 16, and 60; CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; CI Pigment Orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI Pigment Green 7, 19, 21, 26, 36, 58, and 59 as pigments included in the colorant.

[0046] In exemplary embodiments, the brightness, heat resistance, and light resistance of a colored photosensitive composition containing no pigment in the colorant can be further improved. Furthermore, the brightness, heat resistance, and light resistance can be further improved depending on the type and content of additives used in combination with the colorant.

[0047] <Additives>

[0048] The additive may be represented by Chemical Formula 1 below.

[0049] [Chemical Formula 1]

[0050] (X + ) n (Y) m-

[0051] In the above Chemical Formula 1, X includes a heterocyclic ring, and Y includes one or more elements selected from the group consisting of tungsten (W), molybdenum (Mo), silicon (Si), germanium (Ge), arsenic (As), and phosphorus (P), and an oxygen atom.

[0052] Furthermore, n and m are arbitrary integers. For example, n and m can be integers of 1 to 10.

[0053] In an exemplary embodiment, the heterocycle of Chemical Formula 1 includes a cationic atom with a formal charge of +1. The cationic atom may be one of nitrogen (N), carbon (C), sulfur (S), and phosphorus (P). By including a cationic atom with a formal charge of +1, the heterocycle can help stabilize the additive.

[0054] Furthermore, the cationic atom may be an atom constituting a heterocyclic ring, and the positive charge present on the cationic atom may be delocalized within the ring. For example, the positive charge may be delocalized via a conjugated system or a hyperconjugated system. The hyperconjugated system may include carbon-carbon bonds or carbon-heteroatom bonds constituting the ring.

[0055] In addition, in addition to the atoms constituting the ring, the above-mentioned cationic atoms can form covalent bonds with one or more functional groups selected from the group consisting of hydrogen, C1-C10 straight-chain alkyl groups, C3-C10 branched-chain alkyl groups, halogen groups, cyano groups, nitro groups, carbonyl groups, sulfonic acid groups, hydroxyl groups, formyl groups, ester groups, carboxyl groups and amino groups.

[0056] Furthermore, by binding a functional group to the cationic atom, the physical and chemical properties of the heterocycle can be adjusted. For example, if the functional group is an electron-withdrawing group, the positive charge of the heterocycle can be further delocalized.

[0057] In exemplary embodiments, the additive can improve both the heat resistance and light resistance of a colored photosensitive composition. If the functional group is a C1-C10 linear alkyl group or a C3-C10 branched alkyl group, the additive can further improve the colorant's reliability. Furthermore, if the functional group is a C1-C6 linear alkyl group, the additive can further enhance the chemical stability of the colored photosensitive composition. If the functional group is a C1 alkyl group, even a relatively small amount of the additive can significantly improve the light resistance of the colored photosensitive composition.

[0058] Saturated heterocycle

[0059] In some exemplary embodiments, the heterocycle of Chemical Formula 1 may include a saturated ring with 5 to 7 ring atoms. For example, the heterocycle may be one of pyrrolidine, piperidine, azepane, phospholane, phosphinane, phosphepane, tetrahydrothiophene, tetrahydro-2H-thiopyran, and thiepane. In some exemplary embodiments, a saturated heterocycle with 5 to 7 ring atoms can help improve the light resistance of the colored photosensitive composition.

[0060] Furthermore, the nitrogen, phosphorus, or sulfur contained in the heterocyclic ring may become a cationic atom through an additional covalent bond. The additional covalent bond may be formed by bonding to a functional group selected from the group consisting of hydrogen, a C1-C10 linear alkyl group, a C3-C10 branched alkyl group, a halogen group, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, a hydroxyl group, a formyl group, an ester group, a carboxyl group, and an amino group.

[0061] For example, the cationic heterocyclic ring may be 1,1-dimethylpiperidine 1,1-Dimethylpiperidine and 1,1-diethylpiperidine Isodialkylpiperidine 1,1-Dimethylpyrrolidine 1,1-Ethylmethylpyrrolidine and 1,1-diethylpyrrolidine Dialkylpyrrolidine 1,1-Dimethylazepine 1,1-Ethylmethylazepine and 1,1-diethylazaalkane dialkylazaalkanes 1,1-Dimethylphosphane (1,1-dimethylphosphinanium) and other dialkylphosphanes 1,1-Ethylmethylphospholane (1,1-ethylmethylphospholanium) and other dialkylphospholanes 1,1-Diethylphosphine (1,1-diethylphosphepanium) and other dialkylphosphine 1-Methyltetrahydro-1H-thiophene (1-methyltetrahydro-1H-thiophenium) and other alkyltetrahydrothiophenes 1-Methylhexahydrothiopyran (1-methylhexahydrothiopyrylium) and other alkyl hexahydrothiopyrylium 1-Methylthiazane (1-methylthiepan-1-ium) and other alkylthiophenes

[0062] Unsaturated heterocyclic ring

[0063] The heterocyclic ring of Chemical Formula 1 may include unsaturated compounds. Furthermore, the nitrogen, phosphorus, or sulfur atoms contained in the heterocyclic ring may become cationic atoms through additional covalent bonds. The additional covalent bonds may be formed by bonding to a functional group selected from the group consisting of hydrogen, a C1-C10 linear alkyl group, a C3-C10 branched alkyl group, a halogen group, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, a hydroxyl group, a formyl group, an ester group, a carboxyl group, and an amino group.

[0064] In an exemplary embodiment, the heterocyclic ring may be an unsaturated nitrogen-containing heterocyclic ring such as pyrazine, pyridine, pyridazine, pyrimidine, pyrrole or imidazole, and the cationic atom may be nitrogen. For example, X in the above chemical formula 1 may be pyrrole Series compounds, pyridine Series compounds and azepines (azepinium) is one of the compounds. The description is based on the series of compounds, but other compounds are not excluded by the following description.

[0065] In an exemplary embodiment, the pyridine The compound may be formed by a nitrogen atom and a C1 to C10 linear alkyl group or a C3 to C10 branched alkyl group forming a covalent bond. In the case of forming a covalent bond with a C1 to C10 linear alkyl group, the cation of the additive (X + ) and anions (Y m- ) can have a denser structure, and the heat resistance and light resistance of the colored photosensitive composition can be further improved with the help of additives.

[0066] Furthermore, if pyridine is used, in which the nitrogen atom is bound to hydrogen, However, if a pyridine having an alkyl group of C11 or higher is used, the density of the additive may be reduced. Specifically, if the C11 or higher alkyl group is bonded to the nitrogen atom, the anion (Y m- ) content is reduced, the light resistance of the colored photosensitive composition may be reduced.

[0067] Therefore, in exemplary embodiments, the nitrogen atom preferably forms an additional covalent bond with a C1-C10 linear or C3-C10 branched alkyl group, more preferably a C1-C6 alkyl group. Furthermore, in some exemplary embodiments, if the nitrogen atom forms an additional covalent bond with a C1 alkyl (methyl) group, even a small amount of additives can further improve the light resistance of the colored photosensitive composition.

[0068] For example, the cation of the additive can be methylpyridine Ethylpyridine Propylpyridine Isopropylpyridine Cyclopropylpyridine Butylpyridine sec-butylpyridine Isobutylpyridine tert-Butylpyridine Cyclobutylpyridine Pentylpyridine sec-pentylpyridine Isoamylpyridine Neopentylpyridine tert-Amylpyridine Cyclopentylpyridine Hexylpyridine Isohexylpyridine 1-(4-Methylpentyl)pyridine 1-(3-methylpentyl)pyridine 1-(2,3-Dimethylbutyl)pyridine 1-(2,3-Dimethylbutan-2-yl)pyridine 1-(2-methylpentan-3-yl)pyridine Cyclohexylpyridine Heptylpyridine sec-heptylpyridine Isoheptylpyridine Neoheptylpyridine tert-Heptylpyridine Cycloheptylpyridine Octylpyridine sec-octylpyridine Isooctylpyridine Neooctylpyridine tert-octylpyridine Cyclooctylpyridine Nonylpyridine sec-nonylpyridine Isononylpyridine Neononylpyridine tert-nonylpyridine Cyclononylpyridine Decylpyridine sec-Decylpyridine Isodecylpyridine Neodecylpyridine tert-Decylpyridine or cyclodecylpyridine Isoalkylpyridine

[0069] In addition, it contains a compound selected from the group consisting of picoline Ethylpyridine Propylpyridine Butylpyridine Isobutylpyridine Pentylpyridine Cyclopentylpyridine Hexylpyridine Cyclohexylpyridine Heptylpyridine Octylpyridine Nonylpyridine and decylpyridine An alkylpyridine from the group consisting of The additive can improve the light resistance of the colored photosensitive composition, comprising a methylpyridine Ethylpyridine Propylpyridine Butylpyridine Pentylpyridine and hexylpyridine An alkylpyridine from the group consisting of The additive can further improve the light resistance of the colored photosensitive composition, even if the colored photosensitive composition contains less picoline The additive can further improve the light resistance of the colored photosensitive composition.

[0070] The heterocyclic ring contained in the additive of the present invention may be a bicyclic compound. In addition, one ring of the heterocyclic ring may be an unsaturated ring, and the other ring of the compound may be a saturated ring. In addition, both rings of the heterocyclic ring may be unsaturated rings.

[0071] In addition, the saturated bicyclic compound may be a fused bicyclic compound, a bridged bicyclic compound, or a spiro compound, and the unsaturated bicyclic compound may be a fused bicyclic compound, or a bicyclic compound in which the rings are covalently bonded. Examples of unsaturated bicyclic compounds include quinoline, indole, cyclopenta[b]pyridine, and cyclopenta[b]pyrrole. In addition, examples of bicyclic compounds in which the rings are covalently bonded include phenylpyridine compounds such as 3-phenylpyridine.

[0072] Polyacid anions

[0073] In the embodiment, Y in the above Chemical Formula 1 is a tungsten-containing heteropoly acid or isopoly acid.

[0074] In addition, in the embodiment, the anion of the additive (Y m- ) is a compound containing an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon, germanium, arsenic and phosphorus and an oxygen atom.

[0075] In addition, in the exemplary embodiment, the anion of the additive (Y m- ) can be a polyacid anion containing tungsten. The above-mentioned polyacid anion can be one of a heteropolyacid anion and an isopolyacid anion. As an example of a heteropolyacid anion or an isopolyacid anion, it can be considered to be selected from α-[PW 12 O 40 ] 3- Keggin-type phosphotungstate anions, such as α-[P2W 18 O 62 ] 6- or β-[P2W 18 O 62 ] 6- Such as Dawson type phosphotungstate anion, α-[SiW 12 O 40 ] 4- ,β-[SiW 12 O 40 ] 4- or γ-[SiW 12 O 40 ] 4- Keggin-type silicotungstate anions, [P2W 17 O 61 ] 10- 、[P2W 15 O 56 ] 12- 、[H2P2W 12 O 48 ] 12- 、[NaP5W 30 O 110 ] 14- 、α-[SiW9O 34 ] 10- ,γ-[SiW 10 O 36 ] 8- 、α-[SiW 11 O 39 ] 8- ,β-[SiW 11 O 39 ] 8- 、[W6O 19 ] 2- 、[W 10 O 32 ] 4- and [WO4] 2-One or a mixture of two or more of the group consisting of.

[0076] In some exemplary embodiments, the additive includes a Keggin-type phosphotungstate anion or a Keggin-type silicotungstate anion. These additives can further improve the heat resistance and light resistance of the colored photosensitive composition compared to conventional additives.

[0077] In an exemplary embodiment, the additive may include an appropriate amount of a polyacid anion. Furthermore, the cationic heterocycle of the additive may form an ionic bond with the polyacid anion, and the cationic heterocycle and the polyacid anion may combine to achieve charge balance in the additive. Furthermore, the additive may be electrically neutral. For example, if the formal charge of the cationic heterocycle is +1 and the formal charge of the polyacid anion is -3, then three equivalents of the cationic heterocycle and one equivalent of the polyacid anion may form an ionic bond and be present in the additive.

[0078] Furthermore, in exemplary embodiments, when the ratio of the colorant content to the additive content is 5 to 20, the light resistance of the colored photosensitive composition can be improved. For example, if the ratio of the colorant content to the additive content is less than 5, the brightness of the colored photosensitive composition may be excessively reduced. On the other hand, if the ratio of the colorant content to the additive content is greater than 20, the light resistance imparted by the additive may be insufficient.

[0079] Therefore, when the ratio of the colorant content to the additive content is 5 to 20, the light resistance of the colored photosensitive composition containing the additive and the colorant is improved, and more preferably, the ratio of the colorant content to the additive content is 6 to 18.

[0080] initiator

[0081] In exemplary embodiments, the initiator is not limited, but may be one or more compounds selected from the group consisting of triazine compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and oxime compounds.

[0082] Examples of triazine compounds 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-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethylidene]-1,3,5-triazine, etc.

[0083] Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one.

[0084] Examples of biimidazole compounds 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, and imidazole compounds in which the phenyl groups at the 4,4',5,5' positions are substituted with alkoxycarbonyl groups.

[0085] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(N,N'-dimethylamino)benzophenone. Examples of thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0086] Examples of anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Examples of initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

[0087] solvent

[0088] Furthermore, various organic solvents used in the technical field of colored photosensitive compositions can be used.

[0089] As examples of the solvent, there can be considered 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 ether acetate, propylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as 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 glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc.

[0090] Furthermore, from the viewpoint of improving coating and drying properties, the solvent may have a boiling point of 100 to 200° C. In exemplary embodiments, esters such as alkylene glycol alkyl ether acetates, ketones, and esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used.

[0091] <Color Filter>

[0092] This specification discloses a color filter including a colored layer formed from a colored photosensitive composition according to an exemplary embodiment. The color filter may include a substrate and a colored pattern formed on the substrate. Furthermore, the colored pattern may be produced using a colored photosensitive composition obtained according to an exemplary embodiment. For example, the colored photosensitive composition may be uniformly applied to a substrate having a pattern formed thereon, and the colored layer may be formed through an additional process.

[0093] The substrate may be transparent. Furthermore, to ensure the stability of the color filter, a substrate with sufficient strength may be used. For example, glass with excellent chemical stability and high strength may be considered. Barriers may be further formed between each colored pattern. Furthermore, a black matrix may be added between each colored pattern. Conventional methods well known in the art may be used to manufacture the color filter.

[0094] <Image Display Device>

[0095] This specification also discloses an image display device including a color filter according to an exemplary embodiment. Specific examples of image display devices include liquid crystal displays (LCDs), organic EL displays (OLEDs), liquid crystal projectors, display devices for game consoles, display devices for portable terminals such as mobile phones, display devices for digital cameras, and display devices for car navigation systems.

[0096] Synthesis example

[0097] Synthesis example 1.

[0098] Butylpyridinium chloride To 5g of butylpyridinium chloride (TCI), 50g of methanol and 10g of water were added until completely dissolved. The resulting solution was then slowly added dropwise to a solution of 27.97g of phosphotungstic acid hydrate (Aldrich, product number P4006) dissolved in 280g of water. After the addition, the mixture was stirred at 25°C to 50°C for 3-4 hours, after which the precipitate was filtered and washed with water. After filtration, the mixture was dried in a vacuum oven at 40°C for 12 hours to obtain the compound represented by the following chemical formula 1-1.

[0099] [Chemical Formula 1-1]

[0100]

[0101] Synthesis example 2

[0102] The same method as in Synthesis Example 1 was used except that 1-ethylpyridinium bromide was used. (1-EthylpyridiniumBromide, manufactured by TCI) to replace butylpyridinium chloride Thus, the compound of the following Chemical Formula 1-2 was synthesized.

[0103] [Chemical formula 1-2]

[0104]

[0105] Synthesis example 3

[0106] The same method as in Synthesis Example 1 was used except that 1-methylpyridine was used. Hexafluorophosphate (1-Methylpyridinium Hexafluorophosphate, manufactured by TCI) was used to replace butylpyridinium chloride. Thus, the compounds of the following Chemical Formulas 1-3 were synthesized.

[0107] [Chemical formula 1-3]

[0108]

[0109] Synthesis example 4

[0110] The same method as in Synthesis Example 1 was used except that 1-hexylpyridine was used. Hexafluorophosphate (1-Hexylpyridinium Hexafluorophosphate, manufactured by TCI) was used to replace butylpyridinium chloride. Thus, the compounds of the following Chemical Formulas 1-4 were synthesized.

[0111] [Chemical formula 1-4]

[0112]

[0113] Synthesis example 5

[0114] The same method as in Synthesis Example 1 was used except that 1-dodecylpyridinium chloride was used. (1-Dodecylpyridinium Chloride, manufactured by TCI) to replace butylpyridinium chloride Thus, the compounds of the following Chemical Formulas 1-5 were synthesized.

[0115] [Chemical Formula 1-5]

[0116]

[0117] Synthesis example 6

[0118] The same method as in Synthesis Example 1 was used except that hexadecylpyridinium chloride was used. Hexadecylpyridinium Chloride Monohydrate (TCI) is used to replace butylpyridinium chloride. Thus, the compounds of the following Chemical Formulas 1-6 were synthesized.

[0119] [Chemical formula 1-6]

[0120]

[0121] Synthesis Example 7

[0122] The same method as in Synthesis Example 1 was used, but 1-hexadecyl-4-methylpyridinium chloride was used. Hydrate (1-Hexadecyl-4-methylpyridinium Chloride Hydrate, manufactured by TCI) to replace butylpyridinium chloride Thus, the compounds of the following Chemical Formulas 1-7 were synthesized.

[0123] [Chemical Formula 1-7]

[0124]

[0125] Synthesis example 8

[0126] In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube were placed 100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether, 8.2 g of azobisisobutyronitrile, 3.1 g of tricyclodecane skeleton monomethacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 55.2 g of 2-ethylhexyl acrylate, 5.9 g of 4-methylstyrene, 85.2 g of glycidyl methacrylate, and 6.0 g of n-dodecylmercaptan. The temperature of the reaction solution was then raised to 80° C. while stirring, and the reaction was allowed to proceed for 4 hours.

[0127] The temperature of the reaction solution was lowered to room temperature, and the atmosphere in the flask was replaced with air from nitrogen. Then, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol, 43.2 g of acrylic acid, and 136 g of propylene glycol monomethyl ether acetate were added dropwise from a dropping funnel over 2 hours, and the mixture was reacted at 100°C for 6 hours. 6.0 g of succinic anhydride was added to the room temperature reaction solution, and the reaction was continued at 80°C for an additional 6 hours to obtain an alkali-soluble resin (B).

[0128] The solid content acid value of the alkali-soluble resin was 36.2 mgKOH / g, the weight average molecular weight Mw measured by GPC was about 7,540, and Tg was -12°C.

[0129] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin were measured by GPC under the following conditions: The ratio of the weight average molecular weight to the number average molecular weight was defined as the molecular weight distribution (Mw / Mn).

[0130] Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

[0131] Column: TSK-GELG4000HXL + TSK-GELG2000HXL (connected in series)

[0132] Column temperature: 40°C

[0133] Mobile phase solvent: THF

[0134] Flow rate: 1.0 ml / min

[0135] Injection volume: 50 μl

[0136] Detector: RI

[0137] Measurement sample concentration: 0.6 wt% (solvent: THF)

[0138] Calibration standard substances: TSK standard polystyrene F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

[0139] Examples and Comparative Examples

[0140] Colored photosensitive compositions of Examples and Comparative Examples were prepared according to the components and contents listed in Tables 1 and 2 below.

[0141] [Table 1]

[0142]

[0143] [Table 2]

[0144]

[0145] The specific structures and names of the compounds and resins used in Tables 1 and 2 are as follows.

[0146] A-1: the compound of the following chemical formula 1-1

[0147] [Chemical Formula 1-1]

[0148]

[0149] A-2: Compound of the following chemical formula 1-2

[0150] [Chemical formula 1-2]

[0151]

[0152] A-3: Compound of the following chemical formula 1-3

[0153] [Chemical formula 1-3]

[0154]

[0155] A-4: Compound of the following chemical formula 1-4

[0156] [Chemical formula 1-4]

[0157]

[0158] A-5: The compound of the following chemical formula 1-5

[0159] [Chemical Formula 1-5]

[0160]

[0161] A-6: The compound of the following chemical formula 1-6

[0162] [Chemical formula 1-6]

[0163]

[0164] A-7: The compound of the following chemical formula 1-7

[0165] [Chemical Formula 1-7]

[0166]

[0167] B: Alkali-soluble resin prepared according to Synthesis Example 8

[0168] X: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

[0169] Y: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, manufactured by Ciba Specialty Chemicals

[0170] Z: 4-Hydroxy-4-methyl-2-pentanone

[0171] Color filter production

[0172] Color filters were produced using the colored photosensitive compositions produced in Examples 1 to 10 and Comparative Examples 1 to 7. The colored photosensitive composition was applied to a glass substrate (manufactured by FOCAM) with a 2-inch (approximately 5 cm) horizontal and vertical length by spin coating, and a thin film was produced by maintaining the temperature at 100°C for 3 minutes. After the film was sufficiently cooled, it was exposed to light using an exposure machine (MA-6; MICROTEC) in an atmospheric atmosphere at 150 mJ / cm 2 The UV light source uses a 1KW high-pressure mercury lamp that includes g, h, and i rays, with an illumination of 30mJ / cm 2 , no special optical filters were used.

[0173] Furthermore, the film that had not been subjected to the development process was further heated at a temperature of about 230° C. for about 20 minutes, thereby manufacturing a color filter. The film thickness of the manufactured color filter was about 2.0 μm.

[0174] Experimental example

[0175] 1. Heat resistance evaluation

[0176] The color filter was heated at 230°C for 2 hours, and the color difference (ΔE * ab). The colorimeter is OSP-SP200 (manufactured by Olympus). ΔE * ab is relative to CIE1976 (L * ,a * ,b * The saturation value of the ) spatial color system is obtained using the following formula. The evaluation results are shown in Table 3.

[0177] △E * ab={(△L)2+(△a)2+(△b)2}1 / 2

[0178] [Heat resistance evaluation criteria]

[0179] ○ (Excellent): △E*ab value is less than 3

[0180] △(good): △E*ab value 3 to 10

[0181] ×(Insufficient): △E*ab value is greater than 10

[0182] 2. Lightfastness evaluation

[0183] The color filter was placed in a light fastness tester (Xe lamp; manufactured by ATLAS) for 24 hours, and the color difference (ΔE *ab). The colorimeter is OSP-SP200 (manufactured by Olympus). ΔE * ab is relative to CIE1976 (L * ,a * ,b * The saturation value of the spatial color system is obtained using the following formula. The evaluation results are shown in Table 4.

[0184] △E * ab={(△L)2+(△a)2+(△b)2}1 / 2

[0185] [Lightfastness evaluation criteria]

[0186] ○ (Excellent): △E*ab value is less than 3

[0187] △(good): △E*ab value 3 to 10

[0188] ×(Insufficient): △E*ab value is greater than 10

[0189] The evaluation results of heat resistance and light resistance of Examples and Comparative Examples are shown in Tables 3 and 4 below.

[0190] [Table 3]

[0191]

[0192] [Table 4]

[0193]

[0194] As shown in Tables 1 to 4 above, the colored photosensitive compositions of the exemplary examples can improve both heat resistance and light resistance by including colorants and additives. Furthermore, referring to Examples 1 and 4, and Comparative Example 1, it was confirmed that the inclusion of a certain amount or more of the additives of the exemplary examples ensured a good level of light resistance.

[0195] Furthermore, referring to Example 1, Example 4, and Example 7, it was confirmed that the shorter the length of the linear chain bonded to the nitrogen atom of the additive, the more improved the light resistance of the colored photosensitive composition.

[0196] Furthermore, referring to the above-mentioned Examples and Comparative Examples, it was confirmed that as the length of the linear chain bonded to the nitrogen atom of the additive becomes longer than C10, the light resistance of the colored photosensitive composition decreases.

Claims

1. A colored photosensitive composition comprising a colorant containing a dye and an additive represented by the following Chemical Formula 1, The content of the dye is 80% by weight or more relative to the total weight of the colorant. Chemical formula 1 (x + )n(Y) m- In the chemical formula 1, X includes a heterocyclic ring, and Y includes one or more elements selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and an oxygen atom. The heterocyclic ring of Chemical Formula 1 contains a cationic atom with a formal charge of +1, The cationic atom is combined with a C1-C10 linear alkyl group or a C3-C10 branched alkyl group, and The ratio of the content of the colorant to the content of the additive is 5 to 20. 2 . The colored photosensitive composition according to claim 1 , wherein the colorant does not contain a pigment. 3 . The colored photosensitive composition according to claim 1 , wherein the cationic atom is any one of nitrogen, carbon, sulfur, and phosphorus. The colored photosensitive composition according to claim 1 , wherein the heterocyclic ring comprises an unsaturated ring having 5 to 7 ring atoms. The colored photosensitive composition according to claim 1 , wherein the heterocyclic ring comprises a bicyclic structure.

6. The colored photosensitive composition according to claim 1, wherein the heterocyclic ring has any one of the structures of pyrazine, pyridine, pyridazine, pyrimidine, pyrrole, and imidazole, the cationic atom is nitrogen, and a C1-C10 linear alkyl group or a C3-C10 branched alkyl group is bonded to the cationic atom. 7 . The colored photosensitive composition according to claim 1 , wherein the cationic atom is bonded to a C1-C6 linear alkyl group. The colored photosensitive composition according to claim 1 , wherein Y is a tungsten-containing heteropoly acid or isopoly acid. 9 . A color filter comprising a colored layer formed from the colored photosensitive composition according to claim 1 . 10 . An image display device comprising the color filter according to claim 9 .

Images