Xanthene-based compound, colored photosensitive resin composition, color filter, and image display device comprising the same

Abstract

A compound represented by Chemical Formula 1 containing a xanthenic backbone, a colored photosensitive resin composition containing the same, a color filter, and an image display device are provided.

Description

Technology Field

[0001] The present invention relates to a xanthenic compound, a colored photosensitive resin composition, a color filter, and an image display device including the same. More specifically, the invention relates to a dye compound comprising a cation comprising a xanthenic backbone, a colored photosensitive resin composition including the same, a color filter, and an image display device. Background Technology

[0003] A color filter can be placed on top of a liquid crystal display (LCD) device or a white organic light-emitting diode (White-OLED) display device to implement a desired color for each pixel. The color filter may include, for example, a black matrix and a coloring pattern corresponding to RGB pixels, and said coloring pattern may be formed through a fine patterning process with a size corresponding to the pixel size of the display device.

[0004] The color pattern of a color filter can generally be formed by forming a photosensitive composition containing a binder resin and a colorant on a substrate, followed by exposure and development processes. Additionally, a baking process may be performed before and after the exposure process to cure and stabilize the color pattern. However, if the color pattern is not cured uniformly, resin residue may occur during the development process or the color pattern may be partially damaged, which may consequently lead to a deterioration of the pattern's mechanical properties. Furthermore, depending on the type of colorant, there is a possibility that under-curing or non-uniform curing of the color pattern may be exacerbated.

[0005] A colored photosensitive composition is a photosensitive composition containing a coloring agent and can be used as a material for forming a colored pattern. To maintain the performance of a color filter, solvent resistance, heat resistance, and light resistance of the colored pattern are important requirements. Korean Registered Patent No. 10-2114951 (Patent Document 1) discloses a colored curable resin composition using a xanthen compound containing a cation having a xanthen backbone having a sulfamoyl group, but the aforementioned properties are still lacking, and research on this is continuing. Prior art literature

[0007] Republic of Korea Registered Patent No. 10-2114951 The problem to be solved

[0008] One objective of the present invention is to provide a dye compound having improved solvent resistance, heat resistance, and light resistance.

[0009] One objective of the present invention is to provide a color filter having improved pattern characteristics and optical reliability.

[0010] One objective of the present invention is to provide an image display device including the color filter. means of solving the problem

[0012] 1. Compound represented by the following chemical formula 1:

[0013] [Chemical Formula 1]

[0014]

[0015] (In the above Chemical Formula 1, at least one of R1 to R4 each independently comprises an ethylenetic double bond at one end and a C1-C comprising an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A saturated hydrocarbon group, or a C6-C containing an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30It is an aromatic hydrocarbon group, and the others are each independently -H or C1-C 30 saturated hydrocarbon group of or C6-C 30 It is an aromatic hydrocarbon group, and

[0016] At least one of the methylene groups (-CH2-) included in the chain other than the terminal of the saturated hydrocarbon group or the aromatic hydrocarbon group is each independently -O-, -CO-, -COO-, -OCO-, -C(H)(OH)-, -NH-, -NR'-, -CONH-, -CONR'-, -OCONH-, -OCONR'-, -NHCOO-, -NR'COO-, -N=CH-, -OC6H4-, C6-C 15 The arylene group of, or C4-C 15 It may be substituted or unsubstituted with a heteroarylene group, provided that adjacent methylene groups are not simultaneously substituted, R5 and R6 are each independently -H or a C1-C6 alkyl group, and R7 to R 11 At least one of them independently -SO3 - , -CO2 - , -SO3H, -SO3R' or -SO2NR'R”, and the remainders are each independently -H, or C1-C6 alkyl groups, and R' and R” are each independently C1-C 10 alkyl group of, C5-C 10 The cycloalkyl group of, or C7-C 10 It is an arylalkyl group).

[0017] 2. In the above 1, at least one of R1 and R3 in Chemical Formula 1 comprises an ethylenetic double bond at one end and a C1-C compound comprising an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A saturated hydrocarbon group, or a C6-C containing an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A compound that is an aromatic hydrocarbon group.

[0018] 3. In the above 1, at least one of R1 and R3 in Chemical Formula 1 is a compound, each independently selected from the group represented by Chemical Formulas 2-1 to 2-6 below:

[0019] [Chemical Formula 2-1]

[0020]

[0021] [Chemical Formula 2-2]

[0022]

[0023] [Chemical Formula 2-3]

[0024]

[0025] [Chemical Formula 2-4]

[0026]

[0027] [Chemical Formula 2-5]

[0028]

[0029] [Chemical Formula 2-6]

[0030]

[0031] In the above chemical formulas 2-1 to 2-6, L1 to L3 are each independently C1-C 20 alkylene group of, C6-C 12 The cycloalkylene group of, C6-C 12 The arylene group of, or C6-C 12 It is a heteroarylene group, and at least one of the methylene groups (-CH2-) included in L1 to L3 may each be independently substituted with -O-, -CO-, -COO-, -OCO-, -C(H)(OH)-, -NH-, -NR'-, -CONH-, -CONR'-, -OCONH-, -OCONR'-, -NHCOO-, or -NR'COO-, or may be unsubstituted, provided that adjacent methylene groups are not simultaneously substituted, and R' is each independently a C1-C5 alkyl group, and R 12 and R 13Each is independently -H or -CH3, plural n are identical or different and are 0 or 1, and -* indicates the bonding position).

[0032] 4. In the above 3, in the above Chemical Formula 1, R1 and R3 are each independently selected from the group represented by the above Chemical Formulas 2-1 to 2-6.

[0033] 5. In the above 3, in the above chemical formulas 2-1 to 2-6, L1 is C1-C 10 A compound selected from the alkylene groups of

[0034] 6. In the above 3, in the above chemical formulas 2-1 to 2-6, L2 and L3 each independently consists of C1-C5 alkylene groups, C6-C 10 The cycloalkylene group and C6-C 10 A compound selected from the arylene groups of

[0035] 7. In the above 6, in the above chemical formulas 2-1 to 2-6, L2 and L3 is a compound, each independently selected from a C1-C3 alkylene group, a cyclohexylene group, and a phenylene group.

[0036] 8. In the above 1, in Chemical Formula 1, R7 to R 11 R 11 -SO3 - , -CO2 - A compound comprising “, -SO3H, -SO3R' or -SO2NR'R”, wherein the remainders are each independently -H or a C1-C3 alkyl group.

[0037] 9. A colored photosensitive resin composition comprising the compound of 1 above.

[0038] 10. A color filter comprising a cured product of the colored photosensitive resin composition of 9 above.

[0039] 11. An image display device including the color filter of 10 above. Effects of the invention

[0041] A compound according to an embodiment of the present invention can improve the solvent resistance, heat resistance, and light resistance of a colored photosensitive resin composition and a cured pattern produced therefrom by introducing a group containing an ethylenically double bond at the terminal end to an amine included in a xanthenic backbone.

[0042] The pattern characteristics and optical reliability of a color filter and an image display device including a cured pattern of the above-mentioned colored photosensitive resin composition can be improved. Specific details for implementing the invention

[0044] With reference to the drawings below, exemplary embodiments of the present disclosure are described in detail so that those skilled in the art can easily practice the present invention. However, this is merely illustrative and the present invention is not limited to the exemplary embodiments described.

[0046] Xanthenic Compounds

[0047] The xanthenic compound according to the embodiments of the present invention is represented by the following chemical formula 1:

[0048] [Chemical Formula 1]

[0049]

[0050] In the above chemical formula 1,

[0051] At least one of R1 to R4 independently comprises an ethylenetic double bond at one end and a C1-C comprising an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A saturated hydrocarbon group, or a C6-C containing an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 It is an aromatic hydrocarbon group, and the others are each independently -H or C1-C 30 saturated hydrocarbon group of or C6-C 30The aromatic hydrocarbon group is, and at least one of the methylene groups (-CH2-) included in the chain other than the terminal of the saturated hydrocarbon group or the aromatic hydrocarbon group is each independently -O-, -CO-, -COO-, -OCO-, -C(H)(OH)-, -NH-, -NR'-, -CONH-, -CONR'-, -OCONH-, -OCONR'-, -NHCOO-, -NR'COO-, -N=CH-, -OC6H4-, C6-C 15 The arylene group of, or C4-C 15 It may be substituted or unsubstituted with a heteroarylene group, provided that adjacent methylene groups are not simultaneously substituted.

[0052] R5 and R6 are each independently -H or a C1-C6 alkyl group, and R7 to R 11 At least one of them independently -SO3 - , -CO2 - , -SO3H, -SO3R' or -SO2NR'R”, and the remainder are each independently -H or a C1-C6 alkyl group.

[0053] R' and R” each independently, C1-C 10 alkyl group of, C5-C 10 The cycloalkyl group of, or C7-C 10 It is an arylalkyl group.

[0054] The compound of Formula 1 above can improve the solvent resistance, heat resistance, and light resistance of the cured pattern of a composition containing it by having at least one of the groups bonded to the amine of the xanthenic backbone have an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end.

[0055] In the above chemical formula 1, the alkyl group may each independently be a straight-chain alkyl group or a branched-chain alkyl group.

[0056] In the above chemical formula 1, the arylene group may be selected from, for example, a phenylene group, a naphthylene group, anthracendiyl group and a fluorendiyl group, and may be a group substituted with or unsubstituted by a C1-C3 alkyl group.

[0057] In the above chemical formula 1, the heteroarylene group may include hetero elements such as nitrogen, boron, oxygen, sulfur, etc., and may be selected from, for example, a pyrrole group, a pyridazine diyl group, a pyrimidine diyl group, a quinolinylene group, an isoquinolinylene group, a furandyl group, a thiophene diyl group, and a benzothiophenidiyl group, and may be a group substituted with or unsubstituted with a C1-C3 alkyl group.

[0058] In the above chemical formula 1, at least one of R1 and R2 may have its terminals substituted with -COOH or unsubstituted.

[0059] In some embodiments, at least one of R1 and R3 in Formula 1 each independently comprises an ethylenetic double bond at one end and a C1-C comprising an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A saturated hydrocarbon group, or a C6-C containing an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 It can be an aromatic hydrocarbon group.

[0060] In some embodiments, the ethylenetic double bond may be, for example, a double bond of a methacrylate group, an acrylate group, a methacryloyl group, or an acryloyl group.

[0061] In some embodiments, at least one of R1 and R3 in Formula 1 may each independently be selected from the group represented by Formulas 2-1 to 2-6 below:

[0062] [Chemical Formula 2-1]

[0063]

[0064] [Chemical Formula 2-2]

[0065]

[0066] [Chemical Formula 2-3]

[0067]

[0068] [Chemical Formula 2-4]

[0069]

[0070] [Chemical Formula 2-5]

[0071]

[0072] [Chemical Formula 2-6]

[0073]

[0074] In the above chemical formulas 2-1 to 2-6,

[0075] L1 to L3 are each independently, C1-C 20 alkylene group of, C6-C 12 The cycloalkylene group of, C6-C 12 The arylene group of, or C6-C 12 The heteroarylene group is a methylene group (-CH2-) included in L1 to L3, and at least one of the methylene groups (-CH2-) may each be independently substituted or unsubstituted with -O-, -CO-, -COO-, -OCO-, -C(H)(OH)-, -NH-, -NR'-, -CONH-, -CONR'-, -OCONH-, -OCONR'-, -NHCOO-, or -NR'COO-, provided that adjacent methylene groups are not simultaneously substituted.

[0076] R' is independently a C1-C5 alkyl group, and R 12 and R 13 Each is independently -H or -CH3. Multiple n are the same or different, 0 or 1, and -* indicates the bonding position.

[0077] In some embodiments, R1 is C1-C 20 alkyl group or C6-C20 It is an aryl group, and R3 may be a group selected from the groups represented by the above chemical formulas 2-1 to 2-6, wherein the above C1-C 20 The alkyl group of or the C6-C 20 The terminal end of the aryl group can be substituted with -COOH or unsubstituted.

[0078] In some embodiments, in Formula 1, R1 and R3 may each be independently selected from the group represented by Formulas 2-1 to 2-6. Accordingly, the compound of Formula 1 can improve solvent resistance, heat resistance, and light resistance overall without reducing compatibility with other components in the colored photosensitive resin composition.

[0079] In some embodiments, R1 and R3 in Chemical Formula 1 may be the same.

[0080] In some embodiments, in the formulas 2-1 to 2-6, L1 is C1-C 10 It can be selected from the alkylene groups.

[0081] In some embodiments, in the formulas 2-1 to 2-6, L2 and L3 each independently consists of C1-C5 alkylene groups, C6-C 10 The cycloalkylene group and C6-C 10 It can be selected from the arylene groups.

[0082] In some embodiments, in the formulas 2-1 to 2-6, L2 and L3 can each be independently selected from C1-C3 alkylene groups, cyclohexylene groups, and phenylene groups.

[0083] In some embodiments, in Formula 1, R7 to R 11 R 11 -SO3 - , -CO2 -, -SO3H, -SO3R' or -SO2NR'R”, and the remainder may each independently be -H or a C1-C3 alkyl group.

[0084] In some embodiments, for example, R7 to R 11 R 11 -SO3 - is, and the rest can be -H.

[0086] Colored Photosensitive Resin Composition

[0087] The colored photosensitive resin composition according to the embodiments of the present disclosure comprises the compound of Formula 1 described above.

[0088] The above colored photosensitive resin composition may include a coloring agent (A) comprising a compound of Formula 1, a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

[0089] The above colored photosensitive resin composition may further include an additive (E) and / or a solvent (F).

[0090] The coloring agent (A) may include the compound of Formula 1 alone, or may include the compound of Formula 1 and a dye and / or pigment.

[0091] In some embodiments, the coloring agent (A) may include a first coloring agent and a second coloring agent, the first coloring agent may include a compound of Formula 1, and the second coloring agent may include at least one of a dye and a pigment.

[0092] In some embodiments, the weight ratio of the first colorant and the second colorant may be, for example, 1:99 to 45:55, or 1:99 to 30:70.

[0093] The dyes that may additionally be included may be compounds comprising, for example, nitro, nitroso, xanthen, triarylmethane, cyanine, pyranine, squarillium, coumarin, BODYPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene), perylene, fluorescein, anthraquinone, anthracene, azo, quinophthaline, indoline, pyrrolopyrrol, quinoneimine, pyrazol, quinoline, azomethine, stilbene, acridine, azine, oxazine, naphthaamide, benzoquinone, naphthoquinone, porphyrin, phthalocyanine, naphthalocyanine, indigo, diimonium, naphthol, metal complexes, and derivatives thereof as a matrix. The dyes may be, for example, CI solvent yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI Dispulse Yellow 54, 76; CI Solvent Orange 41, 54, 56, 99; CI Acid Orange 56, 74, 95, 108, 149, 162; CI Reactive 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 Bat Green 1, etc. may be included, but are not limited thereto.

[0094] Pigments that may additionally be included may include, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and red pigments such as 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, 269; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60; and violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; It may include CI pigment orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; CI pigment green 7, 19, 21, 26, 36, 58, 59, etc.

[0095] For example, based on the total weight of the colored photosensitive resin composition, the content of the coloring agent (A) may be 10% to 60% by weight or 15% to 45% by weight.

[0096] Suzy (B)

[0097] The resin (B) is not particularly limited but may be an alkali-soluble resin.

[0098] The above alkali-soluble resin (B) may be a copolymer of a monomer mixture comprising a first monomer selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride and a second monomer copolymerizable therewith.

[0099] The first monomer may include, for example, one or more types such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, etc.

[0100] The second monomer is, for example, an aromatic vinyl compound such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, indene, etc.; Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, Unsaturated carboxylic acid ester compounds such as methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, isobornyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate; Unsaturated aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylaminopropyl (meth)acrylate, 3-aminopropyl (meth)acrylate, and 3-dimethylaminopropyl (meth)acrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate and glycidyl methacrylate; vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;It may include one or more types of unsaturated ether compounds such as vinylmethyl ether, vinylethyl ether, and allylglycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amide compounds such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and maleimide compounds such as N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0101] For example, the acid value of the alkali-soluble resin (B) may be 10 mg KOH / g to 200 mg KOH / g, and may be 10 mg KOH / g to 150 mg KOH / g.

[0102] For example, the weight-average molecular weight (Mw) of the alkali-soluble resin (B) may be 3,000 to 30,000.

[0103] For example, based on the total weight of the colored photosensitive resin composition, the content of the alkali-soluble resin (B) may be 5% to 50% by weight or 5% to 30% by weight.

[0104] Polymerizable compound (C)

[0105] The above polymerizable compound (C) may include monofunctional and / or polyfunctional ethylenically unsaturated bond-containing compounds (e.g., (meth)acrylate-based compounds).

[0106] The above polymerizable compound (C) may include one or more compounds containing monofunctional, difunctional, or trifunctional ethylenically unsaturated bonds. The above polymerizable compound (C) may include, for example, one or more of 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0107] For example, based on the total weight of the colored photosensitive resin composition, the content of the polymerizable compound (C) may be 1% to 40% by weight or 2% to 20% by weight.

[0108] Polymerization initiator (D)

[0109] The polymerization initiator (D) can induce a cross-linking reaction of the photopolymerizable compound described above to provide curing pattern characteristics.

[0110] The polymerization initiator (D) may include, for example, an acetophenone-based initiator, a benzophenone-based initiator, a benzoin-based initiator, a thioxantone-based initiator, a triazine-based initiator, an oxime-based initiator, etc.

[0111] The polymerization initiator (D) is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2-isopropylthioxantone, 2,4-diethylthioxantone, 2,4-dichlorothioxantone, It may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, etc.

[0112] For example, based on the total weight of the colored photosensitive resin composition, the content of the polymerization initiator (D) may be 0.01 wt% to 7 wt% or 0.01 wt% to 5 wt% or 0.01 wt% to 2 wt%.

[0113] Additives (E)

[0114] The above additive (E) may include an antioxidant or ultraviolet absorber, a surfactant, an adhesion promoter, a leveling agent, etc.

[0115] The above additive (E) may include, for example, ultraviolet absorbers such as benzotriazole compounds, alkyl phenol compounds, alkoxybenzophenone compounds, phenolic antioxidants, phosphorus-based antioxidants, silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methoxyloyloxypropyltrimethoxysilane, 3-methoxyloyloxypropyltrimethoxysilane, 3-methoxyloyloxypropyltriethoxysilane, 3-methoxyloyloxypropyltriethoxysilane, etc., silane compounds.

[0116] For example, the content of the additive (E) may be 0.05 weight% to 2 weight% based on the total weight of the colored photosensitive resin composition.

[0117] Solvent (F)

[0118] The solvent may include an organic solvent that has solubility for the alkali-soluble resin described above and can provide coating properties for the colored photosensitive resin composition.

[0119] For example, ether-based solvents, acetate-based solvents, aromatic hydrocarbon-based solvents, ketone-based solvents, alcohol-based solvents, and / or ester-based solvents may be used. Examples of the above ether-based solvents include ethylene glycol monoalkyl ether compounds, diethylene glycol dialkyl ether compounds, propylene glycol monomethyl ether, etc. Examples of the above acetate-based solvents include alkyl acetate, alkoxyalkyl acetate, ethylene glycol acetate, propylene glycol methyl ether acetate, etc. Examples of the above aromatic hydrocarbon-based solvents include benzene, toluene, xylene, etc. Examples of the above ketone-based solvents include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples of the above alcohol-based solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, etc.

[0120] The amount of the solvent may be appropriately adjusted considering the sufficient solubility of the alkali-soluble resin and the applicability of the composition, and may be included as a remainder of the colored photosensitive resin composition. As used herein, the term "remainder" is used in an open sense, adjustable according to components and additives added in variable amounts.

[0121] As a non-limiting example, the content of the solvent may be, for example, 10% to 70% by weight or 15% to 65% by weight based on the total weight of the colored photosensitive resin composition.

[0122] According to exemplary embodiments, a colored photosensitive resin composition can be prepared as follows.

[0123] In some embodiments, the dye (A) may be dissolved in the solvent to prepare a coloring solution. The resin (B), the polymerizable compound (C), and the polymerization initiator (D) may be added to and stirred in the coloring solution to prepare the colored photosensitive resin composition.

[0125] Color Filter and Image Display Device

[0126] Embodiments of the present invention provide a color filter comprising a cured pattern prepared from a colored photosensitive resin composition and said cured pattern (which may be referred to as a colored pattern). For example, a colored layer may be formed by coating a colored photosensitive resin composition on a semiconductor substrate such as a glass substrate or a silicon wafer. To this end, methods such as spin coating, slit coating, or inkjet printing may be used, and a colored layer may be formed through a pre-baking or soft-baking process.

[0127] For example, an alkali-soluble resin can be utilized during the pre-baking or soft-baking process to promote deep curing of the coloring layer, after which a desired coloring pattern can be formed by performing exposure and development processes. To form the coloring pattern, a photomask and a light source (g-line, i-line, etc.) can be used to selectively expose the area, and then the unexposed areas can be removed through the development process. Additionally, a post-exposure baking (PEB) process can be performed to improve the mechanical stability of the pattern.

[0128] For example, an aqueous solution of an alkaline compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, or tetramethylammonium hydroxide (TMAH) can be used as the developer for the development process. The formed coloring pattern can be implemented individually for each RGB color, thereby enabling the manufacture of a color filter. Additionally, the coloring pattern can be formed to correspond to each pixel of an image display device, and a black matrix can be formed between adjacent coloring patterns to prevent light interference.

[0129] Embodiments of the present invention provide an image display device comprising the color filter, wherein the image display device may include a structure in which the color filter is disposed on a display panel. The display panel may be, for example, a liquid crystal display (LCD) panel or a white organic light-emitting diode (W-OLED) panel, but is not limited thereto.

[0131] Hereinafter, experimental examples including preferred embodiments and comparative examples are presented to aid in understanding the present invention; however, these are merely illustrative of the invention and are not intended to limit the appended claims. Various changes and modifications are possible within the scope and spirit of the present invention, and all such variations and modifications should be understood to be included within the appended claims.

[0133] Synthetic example

[0135] Synthesis Example 1

[0136] (1) 300 parts by weight of N-methyl-2-pyrrolidone (NMP) were added to a flask equipped with a stirrer, thermometer, reflux condenser, dropping lot and nitrogen inlet tube, and starting material X1 and 4-bromo-butyrate ethyl ester were added in a molar ratio of 1:2 and reacted at 100°C for 4 hours.

[0137] Afterwards, sodium chloride was added at a molar ratio of 2 times to starting material X1 at room temperature and maintained for 1 hour.

[0138] Afterward, the solvent was removed from the obtained mixture by distillation using a rotary evaporator, and then a small amount of methanol was added and vigorously stirred.

[0139] Subsequently, the obtained mixture was added to a mixture of 375 parts ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were filtered, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60°C to obtain the intermediate compound X-1.

[0140] (2) 100 parts by weight of toluene were added to a flask equipped with a stirrer, thermometer, reflux condenser, dropping lot and nitrogen inlet tube, and the intermediate compound X-1 and 2-hydroxy-3-phenoxypropyl acrylate were added in a molar ratio of 1:2.

[0141] Afterward, parts by weight of H2SO45 were slowly added dropwise to the flask over a period of 1 hour, then the temperature was raised to 100°C and the reaction was carried out for 6 hours. After the solvent was removed by distillation of the obtained product using a rotary evaporator, a small amount of methanol was added and the mixture was stirred vigorously.

[0142] Subsequently, the obtained product was added to a mixture of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were filtered, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60°C to obtain a xanthen dye represented by the chemical formula 1-1.

[0144] <Starting Material X1>

[0145]

[0146] Chemical Formula: C 35 H 30 N2O4S

[0147] Exact Mass: 574.19

[0148] Molecular Weight: 574.70

[0149] m / z: 574.19 (100.0%), 575.20 (37.9%), 576.19 (4.5%), 576.20 (4.3%), 576.20 (2.7%), 577.19 (1.7%)

[0150] Elemental Analysis: C, 73.15; H, 5.26; N, 4.87; O, 11.14; S, 5.58

[0152] [Chemical Formula 1-1]

[0153]

[0154] Identification of the compound represented by Chemical Formula 1-1

[0155] (Mass Spectrometry) Ionization Mode

[0156] ESI ＋ :m / z= [M+H] + 1154.42(100.0%), 1155.43(73.8%), 1156.43(30.3%), 1157.43(8.8%), 1156.42(5.1%), 1157.42(3.4%), 1158.43(2.1%), 1155.42(1.5%), 1158.44(1.1%)

[0157] Exact Mass 1154.42

[0159] Synthesis Example 2

[0160] (1) Intermediate compound X-1 was obtained by the same method as in Synthesis Example 1.

[0161] (2) A xanthen dye represented by the following chemical formula 1-2 was obtained by the same method as in Synthesis Example 1, except that 100 parts by weight of toluene were added to a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, and the intermediate compound X-1 and glycerol diacrylate were added in a molar ratio of 1:2.

[0162] [Chemical Formula 1-2]

[0163]

[0164] Identification of compounds represented by chemical formula 1-2

[0165] (Mass Spectrometry) Ionization Mode

[0166] ESI+:m / z= [M+H]+ 1110.38(100.0%), 1111.39(67.3%), 1112.39(25.6%), 1113.39(7.4%), 1112.38(5.5%), 1113.38(3.1%), 1111.38(1.5%), 1114.38(1.2%)

[0167] Exact Mass 1110.38

[0169] Synthesis Example 3

[0170] (1) Intermediate compound X-1 was obtained by the same method as in Synthesis Example 1.

[0171] (2) A xanthen dye represented by the following chemical formula 1-3 was obtained by the same method as in Synthesis Example 1, except that 100 parts by weight of toluene were added to a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, and the intermediate compound X-1 and 2-hydroxy-3-2-hydroxy-3-(4-phenylphenoxy)propyl acrylate were added in a molar ratio of 1:2.

[0172] [Chemical Formula 1-3]

[0173]

[0174] Identification of compounds represented by chemical formula 1-3

[0175] (Mass Spectrometry) Ionization Mode

[0176] ESI ＋ :m / z= [M+H] + 1306.49(100.0%), 1307.49(87.6%), 1308.49(40.7%), 1309.50(10.5%), 1309.49(7.0%), 1308.48(4.5%), 1310.50(3.3%), 1310.49(2.0%)

[0177] Exact Mass 1306.49

[0179] Synthesis Example 4

[0180] In Synthesis Example 1, a xanthenic compound of the following formula X2 was synthesized by the same method, except that 5-hydroxy 2-phentanone was used instead of 2-hydroxy-3-phenoxypropyl acrylate.

[0181] [Chemical Formula X2]

[0182]

[0184] Synthesis Example 5: Synthesis of Alkali-Soluble Resin

[0185] 100 parts by weight of propylene glycol monomethyl ether acetate, 100 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of AIBN, 15 parts by weight of vinyltoluene, 20.0 parts by weight of 2-phenylthioethyl acrylate, 3 parts by weight of methyl methacrylate, and 30 parts by weight of methacrylic acid were added to a flask equipped with a stirrer, thermometer, reflux condenser, dropping lot, and nitrogen inlet, and nitrogen was introduced. Subsequently, the temperature of the reaction mixture was raised to 80°C while stirring and reacted for 6 hours. Afterward, 15 parts by weight of glycidyl methacrylate were added to the resulting reaction mixture, the temperature was raised to 110°C, and reacted for 4 hours. The solid dispersion acid value of the alkali-soluble resin synthesized therefrom was 71.9 mgKOH / g, and the weight-average molecular weight (Mw) measured by GPC was approximately 12,160.

[0187] Preparation Example

[0189] Preparation Example 1: Xanthene dye dispersion A-1

[0190] 10 parts by weight of the xanthene dye of Formula 1-1 prepared in Synthesis Example 1 above, 5 parts by weight of a dispersant (BYKLPN-6919, BYK) (calculated based on solid content), 10 parts by weight of propylene glycol monomethyl ether acetate, and 75 parts by weight of diacetone alcohol were mixed, and 300 parts by weight of 0.2 mm zirconia beads were added and mixed and dispersed to obtain xanthene dye dispersion A-1.

[0192] Preparation Example 2: Xanthene dye dispersion A-2

[0193] 10 parts by weight of the xanthene dye of Formula 1-2 prepared in Synthesis Example 2 above, 5 parts by weight of a dispersant (BYKLPN-6919, BYK) (calculated based on solid content), 10 parts by weight of propylene glycol monomethyl ether acetate, and 75 parts by weight of diacetone alcohol were mixed, and 300 parts by weight of 0.2 mm zirconia beads were added and mixed and dispersed to obtain xanthene dye dispersion A-2.

[0195] Preparation Example 3: Xanthen dye dispersion A-3

[0196] 10 parts by weight of the xanthene dye of Formula 1-3 prepared in Synthesis Example 3 above, 5 parts by weight of a dispersant (BYKLPN-6919, BYK Co.) (calculated based on solid content), 10 parts by weight of propylene glycol monomethyl ether acetate, and 75 parts by weight of diacetone alcohol were mixed, and 300 parts by weight of 0.2 mm zirconia beads were added and mixed and dispersed to obtain xanthene dye dispersion A-3.

[0198] Preparation Example 4: Xanthene dye dispersion A-4

[0199] 10 parts by weight of starting material X1, xanthen dye, 5 parts by weight of dispersant (BYKLPN-6919, BYK) (calculated based on solid content), 10 parts by weight of propylene glycol monomethyl ether acetate, and 75 parts by weight of diacetone alcohol were mixed, and 300 parts by weight of 0.2 mm zirconia beads were added and mixed and dispersed to obtain xanthen dye dispersion A-4.

[0201] Preparation Example 5: Blue pigment dispersion A-5

[0202] Blue pigment dispersion A-5 was prepared by mixing and dispersing 12.0 parts by weight of CI Pigment Blue 15:6 (FASTOGEN® BLUE AE-8K, DIC) as a pigment, 8.0 parts by weight of a dispersant (BYKLPN-6919, BYK) (calculated based on solid content), 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 67.0 parts by weight of propylene glycol monomethyl ether acetate in a bead mill for 12 hours.

[0204] Preparation Example 6: Red pigment dispersion A-6

[0205] A red pigment dispersion A-6 was prepared in the same manner as in Preparation Example 5, except that CI Pigment Red 254 (BK-CF, BASF) was used instead of CI Pigment Blue 15:6 as the pigment.

[0207] Preparation Example 7: Xanthene dye dispersion A-7

[0208] 10 parts by weight of the xanthene dye of formula X2 prepared in Synthesis Example 4 above, 5 parts by weight of a dispersant (BYKLPN-6919, BYK) (calculated based on solid content), 10 parts by weight of propylene glycol monomethyl ether acetate, and 75 parts by weight of diacetone alcohol were mixed, and 300 parts by weight of 0.2 mm zirconia beads were added and mixed and dispersed to obtain xanthene dye dispersion A-7.

[0210] Examples and Comparative Examples

[0212] Colored photosensitive resin compositions according to the examples and comparative examples were prepared by mixing the components listed in Table 1 below in their respective amounts. At this time, each amount is a percentage value based on the total weight of the colored photosensitive composition.

[0213] Composition (wt%) Examples Comparative example 1 2 3 4 5 1 2 3 Colorant (A) A-1 40 20 20 A-2 40 A-3 40 A-4 40 20 A-5 20 20 A-6 20 A-7 40 Suzy (B) 10 10 10 10 10 10 10 10 Polymerizable compound (C) 15 15 15 15 15 15 15 15 Polymerization initiator (D) 5 5 5 5 5 5 5 5 Additives (E) 1 1 1 1 1 1 1 1 Solvent (F) 29 29 29 29 29 29 29 29

[0215] The components listed in Table 1 above are as follows.

[0216] A-1: Xanthene dye dispersion according to Preparation Example 1

[0217] A-2: Xanthene dye dispersion according to Preparation Example 2

[0218] A-3: Xanthene dye dispersion according to Preparation Example 3

[0219] A-4: Xanthene dye dispersion, which is starting material X1

[0220] A-5: Blue pigment dispersion according to Preparation Example 5 (CI Pgment blue 15:6 dispersion)

[0221] A-6: Red pigment dispersion according to Preparation Example 6 (CI Pgment Red 254 dispersion)

[0222] A-7: Xanthene dye dispersion according to Preparation Example 7

[0223] B: Alkali-soluble resin according to Synthesis Example 5

[0224] C: Polymerizable compound [Nippon Chemical Co., DPHA (Dipentaerythritol Hexacrylate)]

[0225] D : OXE-01(BASF)

[0226] E: Megapak F-554 (Dainipong Ink & Chemical Industry)

[0227] F: PGMEA (propylene glycol monomethyl ether acetate, boiling point 145°C)

[0229] Experimental example

[0230] Color filters were each prepared as follows using the colored photosensitive compositions according to the above-described examples and comparative examples.

[0232] Manufacturing of color filters

[0233] A colored photosensitive resin composition was uniformly coated onto a 2-inch × 2-inch glass substrate (manufactured by Corning, “EAGLE XG”) using a spin coating method. Subsequently, the coated substrate was placed on a heating plate and heated at 100°C for 3 minutes to form a thin film.

[0234] Next, a test photomask was placed on the thin film containing a pattern with a transmittance that changes stepwise from 1% to 100% and a line / space pattern of 1 µm to 50 µm. At this time, the gap between the test photomask and the thin film was set to 100 µm, and ultraviolet light was irradiated at an irradiation dose of 100 mJ / cm² using a 1 KW high-pressure mercury lamp containing g-lines, h-lines, and i-lines as a light source. No separate optical filter was used during ultraviolet irradiation.

[0235] The thin film irradiated with ultraviolet light was developed by immersing it in a KOH aqueous developing solution with a pH of 10.5 for 2 minutes. After development, the glass substrate coated with the thin film was washed with distilled water and dried using nitrogen gas. Subsequently, a color filter was manufactured by heating it in a heating oven set to 230°C for 20 minutes.

[0236] The thickness of the patterned cured film of the colored photosensitive resin composition included in the color filter was measured to be 2.3 μm.

[0238] Experimental Example 1: Evaluation of Contents

[0239] To evaluate the solvent resistance of the manufactured color filter, the color filter was immersed in NMP (1-methyl-2-pyrrolidone) solvent for 30 minutes, and the color change before and after immersion was measured.

[0240] A microscopic spectrophotometer (Model No. OSP-SP2000, Olympus) was used to measure color change. The solvent resistance of the color filter was determined by measuring the CIE color coordinate values ​​before and after immersion, and then using Equation 1 below to calculate the color change value (ΔEab ΔE * ab) was calculated and evaluated according to the following criteria.

[0241] [Equation 1]

[0242] ΔE * ab = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1 / 2

[0244] <Evaluation Criteria>

[0245] ○: ΔE * ab < 3

[0246] △: 3 ≤ ΔE * ab ≤ 5

[0247] ×: 5 < ΔE * ab

[0249] Experimental Example 2: Heat Resistance Evaluation

[0250] To evaluate the color change caused by thermal yellowing of the manufactured color filter, the color filter was heated in a heating oven at 230°C for 2 hours, and the color change before and after heating was measured.

[0251] A microscopic spectrophotometer (Model No. OSP-SP2000, Olympus) was used to measure color change. The solvent resistance of the color filter was determined by measuring the CIE color coordinate values ​​before and after immersion, and then using Equation 1 above to calculate the color change value (ΔE * ab) was calculated and evaluated according to the following criteria.

[0253] Evaluation

[0254] ○: ΔE * ab < 3

[0255] △: 3 ≤ ΔE * ab ≤ 5

[0256] ×: 5 < ΔE * ab

[0258] Experimental Example 3: Lightfastness Evaluation

[0259] To evaluate the lightfastness of the manufactured color filter, the color change before and after exposure was measured after exposing it to light for 200 hours using ATLAS’s SUNTEST CPS+.

[0260] A microscopic spectrophotometer (Model No. OSP-SP2000, Olympus) was used to measure color change. Lightfastness was determined by measuring CIE color coordinate values ​​before and after light exposure, and then using Equation 1 above to calculate the color change value (ΔE * ab) was calculated and evaluated according to the following criteria.

[0261] <Evaluation Criteria>

[0262] ○: ΔE * ab < 3

[0263] △: 3 ≤ ΔE * ab ≤ 5

[0264] ×: 5 < ΔE * ab

[0266] Examples Comparative example 1 2 3 4 5 1 2 3 Content ○ ○ ○ ○ ○ △ △ △ heat resistance ○ ○ ○ ○ ○ X △ △ lightfastness △ △ ○ ○ △ X X X

[0268] Referring to Table 2 above, the color filter prepared using a colored photosensitive resin composition containing compounds according to the examples includes an ethylenically double bond in the dye structure, which can participate in the curing reaction during photocuring, thereby improving solvent resistance, heat resistance, light resistance, and reliability.

[0269] Color filters prepared using colored photosensitive resin compositions according to comparative examples that do not contain the compound of Chemical Formula 1 were evaluated to have one or more of solvent resistance, heat resistance, and light resistance reduced or degraded compared to the examples. If solvent resistance is insufficient, the color pattern may be dissolved or damaged by various solvents used during the display manufacturing process. If heat resistance is low, there is a possibility that the color pattern may discolor or physical properties may deteriorate in high-temperature environments during the process or when driving the display. In addition, if light resistance is insufficient, there is a risk that the color of the color filter may change or fade due to light during prolonged use.

Claims

Claim 1 Compound represented by the following chemical formula 1: [Chemical Formula 1] (In the above Chemical Formula 1, at least one of R1 to R4 each independently comprises an ethylenetic double bond at one end and a C1-C comprising an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A saturated hydrocarbon group, or a C6-C containing an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 It is an aromatic hydrocarbon group, and the others are each independently -H or C1-C 30 saturated hydrocarbon group of or C6-C 30 The aromatic hydrocarbon group is, and at least one of the methylene groups (-CH2-) included in the chain other than the terminal of the saturated hydrocarbon group or the aromatic hydrocarbon group is each independently -O-, -CO-, -COO-, -OCO-, -C(H)(OH)-, -NH-, -NR'-, -CONH-, -CONR'-, -OCONH-, -OCONR'-, -NHCOO-, -NR'COO-, -N=CH-, -OC6H4-, C6-C 15 The arylene group of, or C4-C 15 It may be substituted or unsubstituted with a heteroarylene group, provided that adjacent methylene groups are not simultaneously substituted, R5 and R6 are each independently -H or a C1-C6 alkyl group, and R7 to R 11 At least one of them independently -SO3 - , -CO2 - , -SO3H, -SO3R' or -SO2NR'R”, and the remainders are each independently -H, or C1-C6 alkyl groups, and R' and R” are each independently C1-C 10 alkyl group of, C5-C 10 The cycloalkyl group of, or C7-C 10 It is an arylalkyl group). Claim 2 In claim 1, at least one of R1 and R3 in the above formula 1 each independently comprises an ethylenetic double bond at one end and a C1-C compound comprising an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A saturated hydrocarbon group, or a C6-C containing an ethylenetic double bond at one end and an ethylenetic double bond, a phenyl group, or a biphenyl group at the other end. 30 A compound that is an aromatic hydrocarbon group. Claim 3 In claim 1, at least one of R1 and R3 in Chemical Formula 1 is each independently selected from the group represented by the following Chemical Formulas 2-1 to 2-6, compound: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] [Chemical Formula 2-5] [Chemical Formula 2-6] (In the above chemical formulas 2-1 to 2-6, L1 to L3 are each independently, C1-C 20 alkylene group of, C6-C 12 The cycloalkylene group of, C6-C 12 The arylene group of, or C6-C 12 It is a heteroarylene group, and at least one of the methylene groups (-CH2-) included in L1 to L3 may each be independently substituted with -O-, -CO-, -COO-, -OCO-, -C(H)(OH)-, -NH-, -NR'-, -CONH-, -CONR'-, -OCONH-, -OCONR'-, -NHCOO-, or -NR'COO-, or may be unsubstituted, provided that adjacent methylene groups are not simultaneously substituted, and R' is each independently a C1-C5 alkyl group, and R 12 and R 13 Each is independently -H or -CH3, plural n are identical or different and are 0 or 1, and -* indicates the bonding position). Claim 4 In paragraph 3, in the above chemical formula 1, R1 and R3 are each independently selected from the group represented by the above chemical formulas 2-1 to 2-6, a compound. Claim 5 In paragraph 3, in the above chemical formulas 2-1 to 2-6, L1 is C1-C 10 A compound selected from the alkylene groups of Claim 6 In paragraph 3, in the above chemical formulas 2-1 to 2-6, L2 and L3 each independently consists of C1-C5 alkylene groups, C6-C 10 The cycloalkylene group and C6-C 10 A compound selected from the arylene groups of Claim 7 In claim 6, in the above chemical formulas 2-1 to 2-6, L2 and L3 is a compound, each independently selected from a C1-C3 alkylene group, a cyclohexylene group, and a phenylene group. Claim 8 In claim 1, in Chemical Formula 1, R7 to R 11 R 11 -SO3 - , -CO2 - A compound comprising “, -SO3H, -SO3R' or -SO2NR'R”, wherein the remainders are each independently -H or a C1-C3 alkyl group. Claim 9 A colored photosensitive resin composition comprising the compound of claim 1. Claim 10 A color filter comprising a cured product of the colored photosensitive resin composition of claim 9. Claim 11 An image display device including the color filter of claim 10.

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