KR20220121054A - Colored photosensitive composition, color filter, and image display device comprising the same - Google Patents

Abstract

According to embodiments of the present invention, a colored photosensitive composition, a color filter, and an image display device are provided. The colored photosensitive composition includes a colorant and an additive having a predetermined structure, the colorant includes a dye, and the content of the dye relative to the total weight of the colorant is 80% by weight or more.

Description

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

The present invention relates to a colored photosensitive composition, a color filter, and an image display device including the same. More particularly, it relates to a colored photosensitive composition including a colorant and an additive, a color filter, and an image display device including the same.

A color filter is an optical device widely used in imaging devices, liquid crystal displays, and the like. The color filter may be incorporated in a liquid crystal display to color an image, or may be incorporated in an image pickup device and used to obtain a color image. The manufacturing process of a color filter starts by uniformly coating a photosensitive composition containing a colorant on a substrate on which a black matrix pattern is formed. Specifically, a preliminary firing step of heating and drying the applied photosensitive composition to form a coating film, an exposure step of selectively irradiating ultraviolet rays to the coating film using a mask, and a developing step of dissolving the non-photocured portion using a developer solution is performed to form pixels of each color on the color filter. In addition, a firing step may be added after the pixels that have undergone the development step are heated, if necessary.

The colored photosensitive composition is a photosensitive composition containing a colorant, and can be used as a material for forming a colored pattern. In order to reduce power consumption required for driving an image display device, it is required to develop a color filter having a higher luminance. In addition, considering the trend of weight reduction and thinning of image display devices, the colored photosensitive composition should be able to provide high luminance, high coloring power, and high contrast ratio characteristics. As an extension of that, the use of pigments as colorants continues to increase. However, when the concentration of the pigment is increased, the storage stability or coatability of the colored photosensitive composition may be rather deteriorated. In addition, it may be difficult to manufacture a color filter having sufficient performance due to deterioration in moldability and the like.

Patent Document 1 relates to a coloring composition containing a colorant and a polymerizable compound, and discloses a polymer having a portion where the colorant emits fluorescence and a portion that absorbs the fluorescence. According to patent document 1, it was shown that the coloring composition of patent document 1 has high contrast and is excellent in heat resistance. However, the composition of Patent Document 1 has a limitation in that the concentration of the pigment is significant, and thus storage stability and applicability are limited.

Korean Patent Publication No. 10-2015-0101934

One object of the present invention is to provide a colored photosensitive composition having improved color properties and optical properties.

One object of the present invention is to provide a color filter formed from the colored photosensitive composition and having improved color characteristics and optical characteristics with improved reliability.

An object of the present invention is to provide an image display device including the color filter.

1. colorants including dyes; and an additive represented by the following formula (1), wherein the content of the dye relative to the total weight of the colorant is 80% by weight or more, the colored photosensitive composition:

[Formula 1]

(In Chemical Formula 1, X includes a heterocyclic ring, and Y is at least one selected from the group consisting of tungsten (W), molybdenum (Mo), silicon (Si) germanium (Ge), arsenic (As), and phosphorus (P). elemental and oxygen atoms).

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

3. The colored photosensitive composition of the above 1, wherein the hetero ring of Formula 1 includes a cationic atom having a formal charge of +1, and the cationic atom is any one of nitrogen, carbon, sulfur, or phosphorus.

4. In the above 3, the cationic atom includes hydrogen, a C1 to C10 straight chain alkyl group, a C3 to C10 branched chain alkyl group, a halide group, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, a hydroxyl group, a phospho At least one functional group selected from the group consisting of a push group, an ester group, a carboxyl group, and an amino group is bonded, a colored photosensitive composition.

5. The colored photosensitive composition according to the above 4, wherein the hetero ring comprises an unsaturated ring having 5 to 7 ring atoms.

6. The colored photosensitive composition of the above 5, wherein the hetero ring comprises a bicyclic structure.

7. The above 5, wherein the hetero ring has a structure of any one of pyrazine, pyridine, pyridazine, pyrimidine, pyrrole, or imidazole, the cation source atom is nitrogen, and the cationic atom has C1 to C10 A colored photosensitive composition to which a phosphorus straight-chain or C3 to C10 branched-chain alkyl group is bonded.

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

9. The colored photosensitive composition according to the above 1, wherein Y is a heteropolyacid or isopolyacid containing tungsten.

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

11. A color filter comprising a colored layer formed of the colored photosensitive composition of 1 above.

12. An image display device comprising the color filter of 11 above.

The colored photosensitive composition according to embodiments of the present invention includes a colorant including a dye and an additive, and the content of the dye may be 80% by weight or more based on the total weight of the colorant.

In addition, the colorant may not include a pigment. Accordingly, a colored photosensitive composition having high contrast and luminance can be provided.

The colored photosensitive composition according to exemplary embodiments is compatible with a colorant that is a dye, and includes an additive capable of improving reliability of the colored photosensitive composition. The additive may effectively absorb light energy to increase heat resistance and light resistance of the colored photosensitive composition.

In exemplary embodiments, 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, an additive containing a pyridinium-based cation including a C1 to C10 linear or C3 to C10 branched alkyl group may further improve the light resistance of the colored photosensitive composition and the lifespan of the curli filter.

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

[Formula 1]

In addition, in Formula 1, X includes a heterocyclic ring, Y includes at least one element selected from the group consisting of tungsten, molybdenum, silicon, germanium, arsenic, and phosphorus and an oxygen atom. Hereinafter, each configuration will be described in detail.

<Colorant>

In exemplary embodiments, the colorant comprises a dye.

A dye refers to an organic or inorganic compound that dissolves in a solvent and exhibits color in the ultraviolet, visible and infrared regions. Nitro, nitroso, xanthene, triarylmethane, cyanine, pyranine, squarylium, coumarin, BODYPY (4,4-difluoro-4-bora-3a,4a-diaza-s- indacene), perylene, fluorescein, anthraquinone, anthracene, azo, quinophthaline, indoline, pyrrolopyrrole, quinoneimine, pyrazole, quinoline, azomethine, stilbene, acridine, azine, oxazine , naphthaamide, benzoquinone, naphthoquinone, porphyrin, phthalocyanine, naphthalocyanine, indigo, dimonium, naphthol, metal complexes and derivatives thereof, but is not limited thereto.

As dyes included in colorants, Solvent, Acid, Basic, Reactive, Direct, Dispulse in Color Index [published by The Society of Dyers and Colorists] Compounds classified as Disperse or Vat may be used.

As an example of a specific dye, C.I. Solvent Yellow 25, 79, 81, 82, 83, 89; C.I. Acid Yellow 7, 23, 25, 42, 65, 76; C.I. Reactive Yellow 2, 76, 116; C.I. Direct Yellow 4, 28, 44, 86, 132; C.I. Dispulse Yellow 54, 76; C.I. Solvent Orange 41, 54, 56, 99; C.I. acid orange 56, 74, 95, 108, 149, 162; C.I. Reactive Orange 16; C.I. Direct Orange 26; C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289; C.I. Acid Violet 102; C.I. Solvent Green 1, 5; C.I. acid green 3, 5, 9, 25, 28; C.I. Basic Green 1; C.I. Bat Green 1 and the like can be listed without limitation.

In exemplary embodiments, both the heat resistance and light resistance of the colored photosensitive composition may be improved by using a dye and an additive compatible with each other. In addition, in terms of realizing high brightness, the content of the dye is preferably 80% by weight or more, more preferably 90% or more, and most preferably 99% or more, based on the total weight of the colorant. When only a dye is used as the colorant, heat resistance and light resistance can be further improved.

As the pigment, a known pigment can be used. For example, the use of pigments classified as Pigment in the Color Index (published by The Society of Dyers and Colorists) may be considered. However, in order to realize 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, based on the total weight of the colorant.

In exemplary embodiments, a colorant including an additive and a dye may be compatible to improve light resistance. In addition, even if the colorant does not include a pigment, heat resistance and light resistance of the colored photosensitive composition may be improved by compatibility with the additive.

As an example of a pigment, C.I. red pigments such as 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; C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6,16, 60; C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Orange pigments, such as pigment orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Pigment green 7, 19, 21, 26, 36, 58, 59 and the like can be considered as pigments included in the colorant.

In exemplary embodiments, the luminance, heat resistance, and light resistance of the colored photosensitive composition in which the pigment is not included in the colorant may be further improved. In addition, brightness, heat resistance, and light resistance may be further improved according to the type and content of additives compatible with the colorant.

<Additives>

The additive may be represented by the following formula (1).

[Formula 1]

In addition, in Formula 1, X includes a heterocyclic ring, and Y is selected from the group consisting of tungsten (W), molybdenum (Mo), silicon (Si), germanium (Ge), arsenic (As) and phosphorus (P). one or more elements and an oxygen atom. In addition, in exemplary embodiments, the hetero ring of Formula 1 includes a cationic atom having a formal charge of +1, and the cationic atom is nitrogen (N), carbon (C), sulfur (S), or phosphorus (P). By including a cationic atom having a formal charge of +1, the hetero ring may contribute to stabilization of the additive.

In addition, the cationic atom may be an atom constituting the ring of the heterocyclic ring, and the positive charges appearing on the cationic atom may be delocalized in the ring. For example, the positive charges may be delocalized through a conjugation system or may be delocalized through a hyperconjugation system. The superconjugated system may include a carbon-carbon bond constituting a ring, and a carbon-heteroatom bond.

In addition to the atoms constituting the ring, the cationic atom includes hydrogen, a C1 to C10 linear or C3 to C10 branched chain alkyl group, a halide group, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, a hydroxyl group, a phospho At least one functional group selected from the group consisting of a mil group, an ester group, a carboxyl group, and an amino group may be further covalently bonded.

In addition, by further bonding a functional group to the cationic atom, the physical and chemical properties of the hetero ring may be controlled. For example, if the functional group is an electron-withdrawing group, the positive charge of the hetero ring may be more delocalized.

In exemplary embodiments, both heat resistance and light resistance of the colored photosensitive composition including the additive may be improved. If the functional group is a C1 to C10 linear or C3 to C10 alkyl group, the reliability of the colorant may be further improved by the additive. In addition, if the functional group is a C1 to C6 linear alkyl group, the chemical stability of the colored photosensitive composition may be further increased by the additive, and if it is C1, the light resistance of the colored photosensitive composition is more remarkably improved even with the use of a relatively small amount of the additive. can be

saturated heterocyclic ring

In some exemplary embodiments, the hetero ring of Formula 1 may have 5 to 7 ring atoms and may include a saturated ring. For example, the heterocyclic ring is pyrrolidine, piperidine, azepane, phosphorane, phosphinane, phosphinane, tetrahydro It may be one of tetrahydrothiophene, tetrahydro-2H-thiopyran, or thiephane. In some exemplary embodiments, a saturated hetero ring having 5 to 7 ring atoms may contribute to improving light resistance of the colored photosensitive composition.

In addition, nitrogen, phosphorus, or sulfur included in the hetero ring may become a cationic atom through an additional covalent bond. An additional covalent bond is hydrogen, a C1 to C10 straight or branched chain alkyl group, a halide 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. It may be formed by bonding with one selected functional group.

For example, the heterocyclic ring having cationic property is dialkyl piperidinium such as 1,1-dimethylpiperidinium, 1,1-ethylmethylpiperidinium, and 1,1-diethylpiperidinium, 1, 1-dimethylpyrrolidinium, 1,1-ethylmethylpyrrolidinium, and dialkylpyrrolidinium such as 1,1-diethylpyrrolidinium, 1,1-dimethylazepanium, and 1,1-ethylmethylase Panium and dialkylazepanium such as 1,1-diethylazepanium, dialkylphosphinanium such as 1,1-dimethylphospholanium, and 1,1-ethylmethylphospholanium Dialkylphosphoranium such as nium (1,1-dimethylphospholanium), dialkylphosphipanium such as 1,1-diethylphosphepanium, 1-methyltetrahydro-1H-thiophene Alkyltetrahydrothiophenium such as nium (1-methyltetrahydro-1H-thiophenium), Alkylhexahydrothiopyrylium such as 1-methylhexahydrothiopyrylium, 1-methylthiephenium ( 1-methylthiepan-1-ium) and the like may be alkyl thiephenium.

unsaturated heterocyclic ring

The hetero ring of Formula 1 may include an unsaturated compound. In addition, nitrogen, phosphorus, or sulfur included in the hetero ring may become a cationic atom through an additional covalent bond. Additional covalent bonds include hydrogen, a C1 to C10 straight chain or C3 to C10 branched chain alkyl group, a halide 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. It may be formed by combining with one functional group selected from the group consisting of.

In exemplary embodiments, the hetero ring may be a nitrogen-containing unsaturated heterocyclic ring such as pyrazine, pyridine, pyridazine, pyrimidine, pyrrole, or imidazole, and the cation source atom may be nitrogen. For example, X in Formula 1 may be one of a pyrrolium-based compound, a pyridinium-based compound, or an azepinium-based compound. Hereinafter, the pyridinium-based compound is described based on the description, but other compounds are not excluded by the following description.

In exemplary embodiments, the pyridinium-based compound may form a covalent bond with a linear or C3 to C10 branched alkyl group having a nitrogen atom of C1 to C10. When a covalent bond is formed with a C1 to C10 linear alkyl group, the cation (X ⁺ ) and anion (Y ^m- ) of the additive may have a more dense structure, and the heat resistance and light resistance of the colored photosensitive composition by the additive can be further improved.

In addition, when pyridinium in which hydrogen is bonded to a nitrogen atom is used, the density of the additive may be reduced. Conversely, the use of pyridinium bonded to a C11 or higher alkyl group may lead to limited light resistance. In detail, when the C11 or higher alkyl group is bonded to the nitrogen atom, the content of the anion (Y ^m- ) relative to the total weight of the additive may decrease, thereby reducing the light resistance of the colored photosensitive composition.

Accordingly, in exemplary embodiments, the nitrogen atom preferably forms an additional covalent bond with a C1 to C10 linear or C3 to C10 branched alkyl group, and additionally forms a covalent bond with a C1 to C6 alkyl group. more preferably. In addition, in some exemplary embodiments, when the nitrogen atom and C1 (methyl group) additionally form a covalent bond, the light resistance of the colored photosensitive composition may be further improved even if a small amount of the additive is added.

For example, the cation of the additive may be methylpyridinium, ethylpyridinium, propylpyridinium, isopropylpyridinium, cyclopropylpyridinium, butylpyridinium, secbutylpyridinium, isobutylpyridinium, t-butylpyridinium, Cyclobutylpyridinium, pentylpyridinium, secpentylpyridinium, isopentylpyridinium, neopentylpyridinium, t-pentylpyridinium, cyclopentylpyridinium, hexylpyridinium, isohexylpyridinium, 1- (4 -Methylpentyl)pyridinium, 1-(3-methylpentyl)pyridinium, 1-(2,3-dimethylbutyl)pyridinium, 1-(2,3-dimethylbutan-2-yl)pyridinium, 1- (2-methylpentan-3-yl)pyridinium, cyclohexylpyridinium, heptylpyridinium, secheptylpyridinium, isoheptylpyridinium, neoheptylpyridinium, t-heptylpyridinium, cycloheptylpyridinium, octyl Pyridinium, secoctylpyridinium, isooctylpyridinium, neooctylpyridinium, t-octylpyridinium, cyclooctylpyridinium, nonylpyridinium, secnotylpyridinium, isononylpyridinium, neononylpyridinium, t- Alkylpyridies such as nonylpyridinium, cyclononylpyridinium, decanylpyridinium, secdecanylpyridinium, isodecanylpyridinium, neodecanylpyridinium, or t-decanylpyridinium, cyclodecanylpyridinium may be nium.

In addition, methylpyridinium, ethylpyridinium, propylpyridinium, butylpyridinium, isobutylpyridinium, pentylpyridinium, cyclopentylpyridinium, hexylpyridinium, cyclohexylpyridinium, heptylpyridinium, octylpyridinium , nonylpyridinium, or an additive containing one alkylpyridinium selected from the group consisting of decanylpyridinium can improve the light resistance of the colored photosensitive composition, methylpyridinium, ethylpyridinium, propylpyridinium, butylpyridinium An additive containing one alkylpyridinium selected from the group consisting of dinium, pentylpyridinium, or hexylpyridinium may further improve the light resistance of the colored photosensitive composition, and the additive containing methylpyridinium may be added to the colored photosensitive composition. Even if it is contained in a relatively small amount, the light resistance of the colored photosensitive composition can be further improved.

The hetero ring included in the additive of the present invention may be a bicyclic compound. In addition, a part of the hetero ring may be an unsaturated ring, and another part of the compound may be a saturated ring. Alternatively, all of the bicyclic rings of the hetero ring may be unsaturated rings.

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. bicyclic compound) or a bicyclic compound in which each ring is linked by a covalent bond. As an example of the unsaturated bicyclic compound, quinoline, indole, cyclopenta[b]pyridine, cyclopenta[b]pyrrole, etc. can be considered. have. In addition, as an example of a bicyclic compound in which each ring is connected by a covalent bond, a phenylpyridine-based compound such as 3-phenylpyridine may be considered.

polyacid anion

In embodiments, Y in Formula 1 is a heteropolyacid or isopolyacid including tungsten.

Further, in embodiments, the anion (Y ^m- ) of the additive is a compound having an anion having an oxygen atom and at least one element selected from the group consisting of tungsten, molybdenum, silicon, germanium, arsenic and phosphorus.

Also, in exemplary embodiments, the anion (Y ^m− ) of the additive may be a polyacid anion containing tungsten. The polyacid anion may be one of a heteropolyacid or an isopolyacid anion. As an example of heteropolyacid or isopolyacid anion, α-[PW ₁₂ O ₄₀ ] ^3- , such as Keggin-type phosphotungstate anion, α-[P ₂ W ₁₈ O ₆₂ ] ^6- , or β-[P ₂ Dawson-type phosphotungstic anion such as W ₁₈ O ₆₂ ] ^6- , α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , or γ-[SiW ₁₂ O ₄₀ ] ^4- and Keggin-type silicon tungstate anion, [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ³⁴ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ³⁹ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , and [WO ₄ ] ^2- , or a mixture of two or more species selected from the group consisting of can be considered.

In some exemplary embodiments, the additive contains a Keggin-type phosphotungstate anion or a Keggin-type silicotungstate anion. The additive may further improve the heat resistance and light resistance of the colored photosensitive composition compared to the conventional additive.

In exemplary embodiments, the additive may include an appropriate amount of polyacid anion. In addition, the cationic heterocyclic ring of the additive may form an ionic bond with the polyacid anion, and the cationic heterocyclic ring and the polyacid anion are bonded to the additive to achieve charge balance. Additionally, the additive may be electrically neutral. For example, if the formal charge of the cationic heterocyclic ring is +1 and the formal charge of the polyacid anion is -3, 3 equivalents of the cationic heterocyclic ring may be ionically bonded to 1 equivalent of the polyacid anion to be included in the additive.

Further, in exemplary embodiments, when the content ratio of the colorant to the content of the additive is 5 to 20, the light resistance of the colored photosensitive composition may be improved. For example, when the content ratio of the colorant to the content of the additive is less than 5, the luminance of the colored photosensitive composition may be excessively reduced. Conversely, when the content ratio of the colorant to the content of the additive exceeds 20, the light resistance by the additive may be insufficient.

Therefore, when the content ratio of the colorant to the content of the additive is 5 to 20, the light resistance of the colored photosensitive composition including the additive and the colorant is improved, and it is preferable, and the content ratio of the colorant to the content of the additive is more preferably 6 to 18 .

initiator

In exemplary embodiments, the initiator is not limited, but a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, an anthracene-based compound, and an oxime compound It may be one or more compounds selected from the group consisting of.

As an example of a triazine-based compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- (4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) )ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine and the like can be considered.

As an example of the acetophenone-based compound, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxy Ethoxy)phenyl]-2-methylpropan-1-one, -hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one of oligomers and the like may be considered.

As examples of biimidazole compounds, 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, the phenyl group at the 4,4',5,5' position is a carboalkoxy group An imidazole compound substituted by

As an example of a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned. Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di(N,N'-dimethylamino)-benzophenone, etc. are mentioned. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. This can be considered.

Further, examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. can be considered. Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, titanocene compounds and the like can be considered as examples of the initiator.

menstruum

In addition, various organic solvents used in the technical field of coloring photosensitive compositions can be used.

Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3- Esters, such as methyl methoxypropionate, cyclic esters, such as (gamma)-butyrolactone, etc. can be considered.

In addition, the solvent may be a solvent having a boiling point of 100 to 200° C. from the viewpoint of improving applicability and drying properties. In exemplary embodiments, the use of esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate may be considered.

<Color filter>

The present specification discloses a color filter including a colored layer formed of a colored photosensitive composition according to exemplary embodiments. The color filter may include a substrate and a coloring pattern formed on the substrate. In addition, the colored pattern may be prepared from the colored photosensitive composition obtained according to the exemplary embodiments. For example, the colored photosensitive composition may be uniformly applied on a patterned substrate and formed into a colored layer through an additional process.

The substrate may be transparent. In addition, a substrate having sufficient strength for the stability of the color filter may be used. For example, the use of glass having excellent chemical stability and high strength may be considered. A barrier rib may be further formed between each color pattern. In addition, a black matrix may be added between each color pattern. A conventional method well known in the art may be used for manufacturing the color filter.

<Image display device>

In addition, the present specification further discloses an image display device including a color filter according to exemplary embodiments. As specific examples of the image display device, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, and a display for a digital camera A device, a display device for car navigation, and the like may be considered.

Synthesis example

Synthesis Example 1.

A solution completely dissolved by adding 50 g of methanol and 10 g of water to 5 g of butylpyridinium chloride (manufactured by TCI) is slowly added dropwise to a solution obtained by dissolving 27.97 g of Phosphotungstic acid hydrate (manufactured by Aldrich, product number P4006) in 280 g of water. After dripping, the precipitate is filtered and washed with water after stirring at 25 to 50 degrees for about 3 to 4 hours. After filtration, the mixture was dried in a vacuum oven at 40° C. for 12 hours to obtain a compound of Formula 1-1.

[Formula 1-1]

Synthesis Example 2.

The same procedure as in Synthesis Example 1 was performed, except that 1-Ethylpyridinium Bromide (manufactured by TCI) was used instead of Butylpyridinium chloride to synthesize a compound of Formula 1-2 below.

[Formula 1-2]

Synthesis Example 3.

The same procedure as in Synthesis Example 1 was performed, except that 1-Methylpyridinium Hexafluorophosphate (manufactured by TCI) was used instead of Butylpyridinium chloride to synthesize a compound of Formula 1-3.

[Formula 1-3]

Synthesis Example 4.

The same procedure as in Synthesis Example 1 was performed, except that 1-Hexylpyridinium Hexafluorophosphate (manufactured by TCI) was used instead of butylpyridinium chloride to synthesize a compound of Formula 1-4.

[Formula 1-4]

Synthesis Example 5.

The same procedure as in Synthesis Example 1 was performed, except that 1-Dodecylpyridinium Chloride (manufactured by TCI) was used instead of Butylpyridinium chloride to synthesize a compound of Formula 1-4.

[Formula 1-5]

Synthesis Example 6.

It was carried out in the same manner as in Synthesis Example 1, but instead of Butylpyridinium chloride, Hexadecylpyridinium Chloride Monohydrate (manufactured by TCI) was used to synthesize the compound of Formula 1-4.

[Formula 1-6]

Synthesis Example 7.

The same procedure as in Synthesis Example 1 was performed, except that 1-Hexadecyl-4-methylpyridinium Chloride Hydrate (manufactured by TCI) was used instead of Butylpyridinium chloride to synthesize a compound of Formula 1-4.

[Formula 1-7]

Synthesis Example 8.

100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether, 8.2 g of azobisisobutyronitrile, monomethacrylic of tricyclodecane skeleton in a flask equipped with a stirrer, thermometer reflux cooling tube, dropping funnel and nitrogen introduction tube Rate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) 3.1 g, 2-ethylhexyl acrylate 55.2 g, 4-methylstyrene 5.9 g, glycidyl methacrylate 85.2 g, and n-dodecanthiol 6.0 g were added. do. Thereafter, the temperature of the reaction solution was raised to 80° C. with stirring, and the reaction was allowed to proceed for 4 hours.

The temperature of the reaction solution was lowered to room temperature, and the atmosphere of 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 dripped from the dropping funnel over 2 hours, and it reacted at 100 degreeC for 6 hours. 6.0 g of succinic anhydride was added to the reaction solution at room temperature, and the reaction was further performed at 80° C. for 6 hours to obtain an alkali-soluble resin (B).

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

Measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin was performed under the following conditions by using the GPC method. The ratio of the weight average molecular weight and the number average molecular weight was defined as molecular weight distribution (Mw/Mn).

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40 °C

Mobile phase solvent: THF

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent is THF)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Examples and Comparative Examples

Colored photosensitive compositions according to Examples and Comparative Examples were prepared with the components and contents shown in Tables 1 and 2 below.

Furtherance Example One 2 3 4 5 6 7 8 9 10 coloring agent dyes 21.6 21.6 21.6 21.6 21.6 21.6 21.6 21.6 21.6 19.2 pigment 2.4 additive A-1 1.2 2.4 3.6 A-2 1.2 2.4 3.6 A-3 1.2 2.4 3.6 A-4 2.4 Suzy B 15.6 13.4 11.3 15.6 13.4 11.3 15.6 13.4 11.3 13.4 photopolymerization compound X 4 3.44 2.88 4 3.44 2.88 4 3.44 2.88 3.44 initiator Y 0.64 0.55 0.46 0.64 0.55 0.46 0.64 0.55 0.46 0.55 menstruum Z 56.9 58.5 60.1 56.9 58.5 60.2 56.9 58.5 60.2 58.2

Furtherance comparative example One 2 3 4 5 6 7 coloring agent dyes 21.6 21.6 19.2 21.6 19.2 21.6 19.2 pigment 2.4 2.4 2.4 additive A-5 2.4 2.4 A-6 2.4 2.4 A-7 2.4 2.4 Suzy B 17.85 13.4 13.4 13.4 13.4 13.4 13.4 photopolymerization compound X 4.55 3.44 3.44 3.44 3.44 3.44 3.44 initiator Y 0.73 0.55 0.55 0.55 0.55 0.55 0.55 menstruum Z 55.27 58.5 58.2 58.5 58.2 58.5 58.2

Specific structures and names of the compounds and resins used in Tables 1 and 2 are as follows.

A-1: a compound of formula 1-1

[Formula 1-1]

A-2: a compound of formula 1-2

[Formula 1-2]

A-3: a compound of formula 1-3

[Formula 1-3]

A-4: a compound of formula 1-4

[Formula 1-4]

A-5: a compound of formula 1-5

[Formula 1-5]

A-6: a compound of formula 1-6

[Formula 1-6]

A-7: a compound of formula 1-7

[Formula 1-7]

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

X: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

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

Z: 4-hydroxy-4-methyl-2-pentanone

color filter production

prepared in Examples 1 to 10 and Comparative Examples 1 to 7

A color filter was prepared using the colored photosensitive composition. The colored photosensitive composition was coated on a glass substrate (manufactured by FOCAM) having a width and length of 2 inches (about 5 cm) by spin coating, and maintained at a temperature of 100° C. for 3 minutes to prepare a thin film. After the thin film was sufficiently cooled, ultraviolet rays were irradiated with an exposure dose of 150 mJ/cm 2 (based on 365 nm) in an atmospheric atmosphere using an exposure machine (MA-6; manufactured by SUSS MICROTEC) without a photomask. As the ultraviolet light source, a 1 KW high-pressure mercury lamp containing all of the g, h, and i rays was used, the illuminance was 30 mJ/cm 2 , and no special optical filter was used.

In addition, the thin film that has not been developed was further heated at a temperature of about 230° C. for about 20 minutes to prepare a color filter. The film thickness of the prepared color filter was about 2.0 μm.

Experimental example

1. Heat resistance evaluation

The color filter was heated at a temperature of 230° C. for 2 hours, and the color difference (ΔE ^* ab) before and after heating was measured. The colorimeter was OSP-SP200 (manufactured by OLYMPUS). ΔE ^* ab is a value obtained by the following saturation formula for the CIE 1976 (L ^* , a ^* , b ^* ) spatial color system. The evaluation results are shown in Table 3.

ΔE ^* ab = {(ΔL)2 +(Δa)2+(Δb)2}1/2

[Heat resistance evaluation criteria]

○ (Excellent): △E*ab value is 3 or less

△ (good): △E*ab value is 3 to 10 or less

X (less than): △E*ab value exceeds 10

2. Light fastness evaluation

A color filter was placed in a light resistance meter (Xe lamp; manufactured by ATLAS) for 24 hours, and the color difference (ΔE ^* ab) before and after light irradiation was measured. The colorimeter was OSP-SP200 (manufactured by OLYMPUS). ΔE ^* ab is a value obtained by the following saturation formula for the CIE 1976 (L ^* , a ^* , b ^* ) spatial color system. The evaluation results are shown in Table 4.

ΔE ^* ab = {(ΔL)2 +(Δa)2+(Δb)2}1/2

[Light resistance evaluation criteria]

○ (Excellent): △E ^* ab value is 3 or less

△ (good): △E ^* ab value 3 to 10 or less

X (less than): △E ^* ab value exceeds 10

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

Example Evaluation items One 2 3 4 5 6 7 8 9 10 heat resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ light fastness △ ○ ○ △ ○ ○ ○ ○ ○ △

comparative example Evaluation items One 2 3 4 5 6 7 heat resistance ○ ○ ○ ○ ○ ○ ○ light fastness X △ △ X X X X

According to Tables 1 to 4, the colored photosensitive compositions according to the exemplary embodiments may include a colorant and an additive to improve both heat resistance and light resistance. In addition, referring to Examples 1, 4, and Comparative Example 1, it can be confirmed that a good level of light resistance is secured by including a certain amount or more of the additives according to the exemplary embodiments.

In addition, referring to Examples 1, 4, and 7, it can be seen that the light resistance of the colored photosensitive composition is improved as the length of the straight chain bonded to the nitrogen atom of the additive becomes shorter.

Furthermore, referring to Examples and Comparative Examples, it can be seen that the light resistance of the colored photosensitive composition decreases as the length of the straight chain bonded to the nitrogen atom of the additive exceeds C10.

Claims (12)

colorants including dyes; and
It contains an additive represented by the following formula (1),
The content of the dye relative to the total weight of the colorant is 80% by weight or more, the colored photosensitive composition:
[Formula 1]

(In Formula 1, X includes a heterocyclic ring, Y includes at least one element selected from the group consisting of tungsten (W), molybdenum (Mo), silicon (Si), and phosphorus (P) and an oxygen atom).
According to claim 1,
The colorant does not contain a pigment, a colored photosensitive composition.
According to claim 1,
The heterocyclic ring of Formula 1 includes a cationic atom having a formal charge of +1, and the cationic atom is any one of nitrogen, carbon, sulfur or phosphorus, the colored photosensitive composition.
4. The method of claim 3,
The cationic atom includes hydrogen, a C1 to C10 linear alkyl group, a C3 to C10 branched chain alkyl group, a halide group, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, a hydroxyl group, a formyl group, an ester group carboxyl group, and At least one functional group selected from the group consisting of an amino group is bound, the colored photosensitive composition.
5. The method of claim 4,
The hetero ring is a colored photosensitive composition comprising an unsaturated ring having 5 to 7 ring atoms.
6. The method of claim 5,
The heterocyclic ring comprises a bicyclic structure, the colored photosensitive composition.
6. The method of claim 5,
The hetero ring has a structure of any one of pyrazine, pyridine, pyridazine, pyrimidine, pyrrole, or imidazole, the cation source atom is nitrogen, and the cationic atom is a C1 to C10 straight chain or C3 to C10 A colored photosensitive composition to which a phosphorus branched-chain alkyl group is bonded.
8. The method of claim 7,
A C1 to C6 linear alkyl group is bonded to the cationic atom, the colored photosensitive composition.
According to claim 1,
Wherein Y is a heteropolyacid or isopolyacid containing tungsten, the colored photosensitive composition.
10. The method of claim 9,
The content of the colorant relative to the content of the additive is 5 to 20, the colored photosensitive composition.
A color filter comprising a colored layer formed of the colored photosensitive composition of claim 1 .
An image display device comprising the color filter of claim 11 .