KR101954701B1 - Disazo yellow pigment, pigments dispersion and photosensitive resin composition using the same - Google Patents

Abstract

The present invention relates to a novel disazo compound for a yellow pigment, a pigment dispersion comprising the same, and a photosensitive resin composition. The disazo compound has high heat resistance and excellent dispersibility, thereby improving dispersibility and storage stability of the pigment dispersion comprising the same. Therefore, the photosensitive resin composition using the disazo compound or the pigment dispersion comprising the same can realize excellent coloring power and a high-quality color filter having excellent optical characteristics such as brightness, contrast, and the like is provided.

Description

DISCHARGE YELLOW PIGMENT, PIGMENTS DISPERSION AND PHOTOSENSITIVE RESIN COMPOSITION USING THE SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disazo yellow pigment,

Disclosed is a novel disazo yellow pigment, a pigment dispersion containing the same, and a photosensitive resin composition.

Due to the nature of the display industry, efforts are being made to obtain colors that are closer to nature by implementing sharper colors, distinct contrast and brightness. In order to realize such a high resolution, the role of the color filter among the various key components of the LCD is most important.

As consumers' desire for display devices such as TVs and smart phones becomes increasingly complicated, the development of color materials with enhanced color reproducibility, transmittance, tinting strength, heat resistance, light resistance, and chemical resistance in order to display sharper, It is a core technology challenge.

Of the RGB (Red, Green, Blue) pigments used for color filters, yellow pigments are used for color correction of red and green, and such coloring yellow pigments include C.I. Pigment Yellow 117, 129, 139, 138, 150, 180, 185 and the like are appropriately mixed and used.

As yellow pigments usable in color filters, compounds such as disazo, azo, quinophthalone, azomethine, isoindolin, and benzimidazolone compounds are generally used. Among these, disazo pigments are highly functional pigments with heat resistance, light resistance, chemical resistance and vivid color, and are used in color filters, plastics, inks, paints, etc., and by the combination of disazo derivatives and couplers introduced with various substituents, yellow ), Yellow (golden yellow), orange (yellow), and the like.

Pigment Yellow 180 (PY 180), which is a disazo yellow pigment among yellow pigments currently used for coloring a colorant for a color filter, is prepared by reacting 1, 2-bis [2-aminophenoxy] ethanedis azo compound with acetone Although acetylaminobenzimidazolone is substituted with acetylaminobenzimidazolone, it is known as a yellow pigment excellent in heat resistance. However, it has disadvantages of lacking color reproducibility, transparency and tinting power.

Therefore, in order to improve the competitiveness and technological power of developing color filters and related materials, there is a need for continuous and intensive research and development on color materials having improved heat resistance, light resistance, chemical resistance, color reproducibility, transparency and tint.

JP 2002-012784 A

It is an object of the present invention to provide novel compounds, i.e. novel disazo yellow pigments.

It is still another object of the present invention to provide a pigment dispersion and a photosensitive resin composition comprising a disazo yellow pigment excellent in heat resistance.

Another object of the present invention is to provide a pigment dispersion and a photosensitive resin composition comprising a disazo yellow pigment excellent in dispersibility and coloring power.

It is still another object of the present invention to provide a high-quality color filter which is excellent in transparency, has improved luminance and contrast, and can realize a clearer color.

In order to realize the object of the present invention described above, a compound represented by the following formula (1) is provided.

[Chemical Formula 1]

[In the above formula (1)

R ₁ and R ₂ are each independently a substituted or unsubstituted acetoacetamylbenzooxazole group or a substituted or unsubstituted pyridone group;

R ₃ and R ₄ are each independently selected from halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl C ₁ -C ₂₀ alkyl, hydroxy C ₁ -C ₂₀ alkyl, Halo C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ heteroaryl;

m and n are each independently an integer of 0 to 4, and when m or n is an integer of 2 or more, R ₃ or R ₄ may be the same or different;

Wherein said substitution is selected from the group consisting of halo, hydroxy, cyano, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, halo C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ aryl, and heteroaryl, wherein heterocycloalkyl and heteroaryl are each independently B, N, O, S, Se, -P (= O) -, -C (= O ) -, Si and < RTI ID = 0.0 > P,

The compound of Formula 1 may be used as a yellow pigment.

The compound according to one embodiment of the present invention may be represented by the following formula (2).

(2)

[In the formula (2)

R ₁₁ and R ₁₃ are independently selected from halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy, C ₁ -C ₂₀ alkyl, halo C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ each Aryl or C ₆ -C ₂₀ heteroaryl;

R ₁₂ and R ₁₄ are each independently hydrogen, halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;

L ₁ and L ₂ are each independently a direct bond, C ₆ -C ₂₀ arylene or C ₆ -C ₂₀ heteroarylene;

Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, Se, -P (= O) -, -C (= O)

In Formula 2, L ₁ and L ₂ each independently may be a direct bond or C ₆ -C ₁₂ arylene.

The compound according to one embodiment of the present invention may be represented by the following formula (3).

(3)

[Formula 3]

R ₂₃ and R ₂₇ are each independently C ₁ -C ₂₀ alkyl, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;

_{R 21, R 22, R 24} , R 25, R 26 and R ₂₈ are independently selected from halo, hydroxy, cyano, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy, C ₁ -C ₂₀ each alkyl or halo C ₁ -C ₂₀ alkyl;

R ₃₁ and R ₃₂ are each independently hydrogen, halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;

In Formula 1, m and n may be 0.

In Formula 1, m and n are integers of 1, and R ₃ and R ₄ are each independently C ₁ -C ₇ alkoxy.

Disclosed is a pigment dispersion comprising a compound represented by Formula 1 and a solvent. The pigment dispersion may be used as a yellow pigment dispersion.

In the pigment dispersion according to an embodiment of the present invention, the pigment dispersion may contain 0.01 to 20% by weight of the compound of Formula 1 and the remaining amount of the solvent based on the total weight.

There is provided a colored photosensitive resin composition comprising the compound represented by Formula 1 and a photosensitive binder resin.

In the colored photosensitive resin composition according to one embodiment of the present invention, the colored photosensitive resin composition may further include at least one additive selected from organic pigments, pigment dispersants, photoinitiators, photopolymerizable compounds, solvents and the like.

A color filter is also provided. A color filter according to an embodiment of the present invention includes a colored layer formed by curing the colored photosensitive resin composition.

The compound of formula (I) can be used as a yellow pigment having excellent heat resistance as well as excellent dispersibility and storage stability.

Thus, the pigment dispersion containing the compound of formula (I) does not cause a decrease in transparency and tinting power even at a high temperature, and thus can achieve excellent tinting strength.

In addition, the colored photosensitive resin composition containing the compound of formula (1) is excellent in reproducibility as well as realizing improved transparency and coloring power, and can be usefully used in color filters requiring high resolution.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Hereinafter, the disazo yellow pigment, the pigment dispersion containing the same, and the photosensitive resin composition according to the present invention will be described in detail.

The term "acetoacetamaminobenzoxazole group" used herein means a functional group in which an aromatic ring containing a benzoxazole group is N -substituted in acetoacetamide, and the aromatic ring is a benzooxazole group and a benzoxazole group In which C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ heteroaryl is connected by a direct bond.

The term " alkyl ", as used herein, refers to a functional group derived from hydrocarbons in straight or branched form, including alkyls other than "alkoxy ". In addition, the alkyl and alkyl-containing substituents according to the present invention are preferably those having a short chain of 1 to 7 carbon atoms, preferably methyl, ethyl, propyl, butyl and the like, but are not limited thereto.

The term "arylalkyl" as used herein means a functional group in which at least one of the hydrogen atoms of the alkyl group is substituted with aryl, and "hydroxyalkyl" means a functional group in which at least one hydrogen atom of the alkyl group is substituted with hydroxy And "haloalkyl" means a functional group in which at least one of the hydrogen atoms of the alkyl group is substituted with halogen. Here, halogen means fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

The term "cycloalkyl" as used herein refers to a functional group derived by the removal of one hydrogen from a fully saturated and partially unsaturated hydrocarbon ring of 3 to 6 carbon atoms, and "heterocycloalkyl" O, S, Se, -P (= O) -, -C (= O) -, or a functional group derived by removal of one hydrogen from a fully saturated and partially unsaturated hydrocarbon ring of carbon atoms, Si and P, and the like.

As used herein, the term "aryl" means a functional group derived by removing one hydrogen from an aromatic hydrocarbon ring, including a single or fused ring system, including a plurality of aryls connected by a single bond, "Arylene" means a functional group derived by removal of one hydrogen from the aryl.

The term "heteroaryl" as used herein refers to a functional group derived by removal of one hydrogen from an aromatic hydrocarbon ring and is selected from the group consisting of B, N, O, S, Se, -P (= O) -, Si and P, and "heteroarylene" means a functional group derived by removing one hydrogen from the heteroaryl.

Conventional disazo yellow pigments have been used as colorants for printing inks, paints and plastics due to their high tinting strength and high productivity. However, such a disazo-based yellow pigment has a disadvantage in terms of process stability, in particular, in the case of accompanied by a high-temperature process, transparency and tinting strength are lowered, and reproducibility in tinting strength is remarkably low, despite excellent heat resistance.

Pigment Yellow 180 (P. Y. 180), which is a typical example of a disazo yellow pigment used for toning color materials for color filters, is also excellent in heat resistance but lacks color reproducibility, transparency and tinting strength.

Accordingly, the present inventors have intensively studied the disazo yellow pigment, and as a result, have devised a yellow pigment compound capable of realizing an excellent tinting power with an improved dispersibility as well as an excellent heat resistance like the conventional disazo yellow pigment .

Specifically, the compound according to one embodiment of the present invention is excellent in heat resistance, dispersibility and dispersion stability by introducing an acetoacetaminobenzoxazole group or a pyridone group into a bisphenoxyethanedisazo compound , And significantly improves the compatibility with the solvent. Thus, the compounds according to one embodiment of the present invention are suitable for color filter applications that require high temperature processes as well as conventional colorant applications.

The compound according to one embodiment of the present invention may be represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

R ₁ and R ₂ are each independently a substituted or unsubstituted acetoacetamylbenzooxazole group or a substituted or unsubstituted pyridone group;

R ₃ and R ₄ are each independently selected from halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl C ₁ -C ₂₀ alkyl, hydroxy C ₁ -C ₂₀ alkyl, Halo C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ heteroaryl;

m and n are each independently an integer of 0 to 4, and when m or n is an integer of 2 or more, R ₃ or R ₄ may be the same or different;

Wherein said substitution is selected from the group consisting of halo, hydroxy, cyano, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, halo C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ heteroaryl, wherein heterocycloalkyl and heteroaryl are each independently B, N, O, S, Se, -P (= O) -, -C (= O ) -, Si and < RTI ID = 0.0 > P,

The compound of the formula (1) has excellent heat resistance as well as excellent compatibility (miscibility) with solvents, resins and further organic pigments by introducing an acetoacetaminobenzoxazole group or a pyridone group, so that the dispersibility can be remarkably improved . Accordingly, even in a high-temperature process, the color filter of the display device including the colored layer employing the color filter improved dramatically in transparency and coloring power can realize excellent optical characteristics of brightness and contrast.

The compound according to one embodiment of the present invention may be represented by the following formula (2).

(2)

[In the formula (2)

R ₁₁ and R ₁₃ are independently selected from halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy, C ₁ -C ₂₀ alkyl, halo C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ each Aryl or C ₆ -C ₂₀ heteroaryl;

R ₁₂ and R ₁₄ are each independently hydrogen, halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;

L ₁ and L ₂ are each independently a direct bond, C ₆ -C ₂₀ arylene or C ₆ -C ₂₀ heteroarylene;

Wherein said heteroarylene and heteroaryl comprise at least one heteroatom selected from B, N, O, S, Se, -P (= O) -, -C (= O)

Specifically, in the formula (2), L ₁ and L ₂ each independently may be a direct bond or C ₆ -C ₁₂ arylene, and more specifically, phenyl, naphthyl, biphenyl C ₆ -C ₁₂ aryl may be selected from renil.

The disazo yellow pigment according to an embodiment of the present invention may be represented by the following formula (3).

(3)

[Formula 3]

R ₂₃ and R ₂₇ are each independently C ₁ -C ₂₀ alkyl, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;

_{R 21, R 22, R 24} , R 25, R 26 and R ₂₈ are independently selected from halo, hydroxy, cyano, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy, C ₁ -C ₂₀ each alkyl or halo C ₁ -C ₂₀ alkyl;

R ₃₁ and R ₃₂ are each independently hydrogen, halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;

In order to show the remarkable effect of the above-mentioned effect, the compound for yellow pigment according to one embodiment of the present invention is a compound in which a disazo group containing an acetoacetaminobenzoxazole group or a pyridone group is a phenyl group of bisaminophenoxyethane 2 position or 4 position.

In one embodiment, the compound for a yellow pigment according to the present invention may be a compound in which a disazo group containing an acetoacetaminobenzoxazole group or a pyridone group is substituted at the 2-position of the phenyl group of the mother of the bisphenoxyethane, It is structurally stable and it is possible to secure improved transparency and tinting power.

In one embodiment, the compound for a yellow pigment according to the present invention may be a compound in which a disazo group containing an acetoacetaminobenzoxazole group or a pyridone group is substituted at the 4-position of the phenyl group of the mother of the bisphenoxyethane, Compatibility with the solvent and the photosensitive binder resin is excellent, and stable dispersibility can be ensured.

In the compound according to an embodiment of the present invention, m and n in Formula 1 may be independently 0.

Specifically, in the compound according to an embodiment of the present invention, m and n in Formula 1 are integers of 1, and R ₃ and R ₄ are each independently C ₁ -C ₇ alkoxy.

More specifically, the compound according to one embodiment of the present invention may be selected from the following structures, but is not limited thereto.

Hereinafter, a method of preparing a compound according to an embodiment of the present invention will be described, but it is needless to say that the present invention is not limited as long as it can be recognized by those skilled in the art.

The compound represented by the following general formula (1) is prepared by dispersing a bisaminophenoxyethane derivative represented by the following general formula (4) in water and a mixed solution of acetic acid or propionic acid and acetic acid, stirring the mixture, and then adding hydrochloric acid, sodium nitrite (NaNO ₂ ) (HO ₃ SONO) to prepare a disjoined solution; Dissolving an acetoacetanilide derivative or pyridone derivative in an alkali solution to prepare a coupler solution; And mixing the dispersed solution and the coupler solution at a molar ratio of 1: 2 and stirring the mixture.

[Chemical Formula 1]

[Chemical Formula 4]

[In the above formulas (1) and (4)

R ₁ and R ₂ are each independently a substituted or unsubstituted acetoacetamylbenzooxazole group or a substituted or unsubstituted pyridone group;

R ₃ and R ₄ are each independently selected from halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl C ₁ -C ₂₀ alkyl, hydroxy C ₁ -C ₂₀ alkyl, Halo C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ heteroaryl;

m and n are each independently an integer of 0 to 4, and when m or n is an integer of 2 or more, R ₃ or R ₄ may be the same or different;

Wherein said substitution is selected from the group consisting of halo, hydroxy, cyano, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, halo C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₆ -C ₂₀ aryl or C ₆ -C ₂₀ heteroaryl, wherein heterocycloalkyl and heteroaryl are each independently B, N, O, S, Se, -P (= O) -, -C (= O ) -, Si and < RTI ID = 0.0 > P,

In the above production method, the purification step may further include a step of filtering, washing and drying the reaction solution after the stirring step.

In the above-mentioned production process, the step of producing the disazosified solution, the step of producing the coupler solution, and the step of stirring them may each independently be carried out at a temperature range of -20 to 20 캜, specifically 0 To < RTI ID = 0.0 > 10 C. < / RTI >

In the above production method, the step of stirring may be carried out in the range of pH 6 to 8, specifically in the range of pH 6 to 7.

In the above production method, the alkali solution in the step of producing the coupler solution may be one obtained by dissolving an alkali metal salt in water (distilled water), C ₁ -C ₃ alcohol and a mixed solution thereof. At this time, the alkali metal salt may be a hydroxide, carbonate, hydrogen carbonate, or the like of an alkali metal such as sodium or potassium. Non-limiting examples of the alkali metal salt include sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, .

Disclosed is a pigment dispersion comprising a compound represented by the above formula (1) and a solvent as a yellow pigment.

The pigment dispersion according to one embodiment of the present invention includes the compound of formula (1), thereby making it possible to realize excellent dispersibility in a solvent and to form a stable dispersion with excellent dispersibility even at a high concentration.

The pigment dispersion according to an embodiment of the present invention may further include at least one selected from organic pigments and pigment dispersants. As described above, the pigment dispersion according to the present invention provides a stable pigment dispersion with its own dispersion stability as well as an enhanced binding force with further organic pigments, and achieves a synergistic effect with a pigment dispersant to be added to improve dispersion stability do.

The pigment dispersion according to an exemplary embodiment of the present invention may contain 0.01 to 20% by weight of the compound of Formula 1 and the remaining amount of the solvent based on the total weight of the pigment dispersion. Specifically, 0.01 to 15% by weight of the compound of Formula 1 % And a residual solvent, more specifically 0.01 to 10% by weight of the compound of the formula (1) and a residual amount of the solvent.

The solvent of the pigment dispersion according to an embodiment of the present invention is not limited as long as it is conventional.

In one embodiment, the solvent is selected from the group consisting of aromatic compounds such as toluene, xylene, and ethylbenzene; Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetyl acetone, isophorone, acetophenone, and cyclohexanone; Ethyl acetate - n - butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, ethyl-3-methoxybutyl, ethyl glycol acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, 3 Methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl butyl, ethyl-3-ethoxypropionate , Ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, and 1,3-butylene glycol diacetate; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono - n - propyl ether, ethylene glycol mono - i - propyl ether , diethylene glycol mono - i - propyl ether, ethylene glycol mono -n- butyl ether, diethylene glycol mono - n - butyl ether, triethylene glycol mono - n - butyl ether, ethylene glycol mono - t - butyl ether, di ethylene glycol mono - t - butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono - t - butyl ether, propylene glycol mono - n - propyl ether, propylene Glycol mono- i -propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Soluble glycol ethers such as mono- n -propyl ether, dipropylene glycol mono- i -propyl ether, propylene glycol mono- n -butyl ether and dipropylene glycol mono- n -butyl ether; Ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl Water-insoluble glycol ethers such as ether, dipropylene glycol propyl ether and propylene glycol methyl ether propionate; Alcohols such as ethanol, methanol, butanol, propanol, isopropanol and diacetone alcohol; And aliphatic such as n -pentane, n -hexane and n -heptane; And the like. These solvents may be used alone or in combination of two or more.

The compound represented by the above formula (1); Or a pigment dispersion comprising the compound and a solvent; and a photosensitive binder resin. At this time, the colored photosensitive resin composition may be a colored photosensitive resin composition for a color filter.

In one embodiment, the photosensitive binder resin is not limited as long as it is a conventional one, and as a non-limiting example thereof, a linear polymer polymer may be an acrylic resin soluble in an organic solvent.

Non-limiting examples of monomers usable in the acrylic resin include compounds having at least one carboxyl group in the molecule (e.g., acrylic acid, methacrylic acid, maleic acid, fumaric acid); Aromatic vinyl compounds such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzylmethylether, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and the like; Unsaturated carboxylate compounds (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate); Compounds having a hydroxyl group (e.g., 2-hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate); (Meth) acrylamide, secondary or tertiary Aactyl acrylamide, dialkylaminoalkyl (meth) acrylate, N -vinylpyrrolidone, N -vinylcaprolactam, vinylimidazole, Vinyltriazole); Branched or straight chain butyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate; Other examples of the hydrophilic compound include monomers containing a tetrahydrofurfuryl group, a phosphoric acid moiety, a phosphoric acid ester moiety, a quaternary ammonium salt moiety, an ethyleneoxy chain, a propyleneoxy group and a sulfonic acid group. It is not.

In order to increase the crosslinking efficiency, the acrylic resin may have a polymerizable group in the side chain.

At this time, the molecular weight of the acrylic resin is not particularly limited, but the weight average molecular weight may be 1,000 to 200,000, specifically 2,000 to 50,000.

The colored photosensitive resin composition according to an embodiment of the present invention includes the compound of Formula 1, and thus has excellent heat resistance and is highly compatible with solvents, resins, and additional organic pigments, The colored layer formed by curing the colored photosensitive resin composition can realize excellent transparency and coloring power. Particularly, by significantly improving the transparency and tinting power during the high-temperature process, the display device including the colored layer can realize excellent optical characteristics in terms of brightness and contrast.

The colored photosensitive resin composition according to one embodiment of the present invention may contain 0.01 to 20% by weight of the compound of Formula 1 and 0.1 to 20% by weight of the photosensitive binder resin based on the total weight of the composition, specifically 0.05 To 10% by weight of a compound of formula (I) and 0.1 to 20% by weight of a photosensitive binder resin, more specifically 0.1 to 5% by weight of a compound of formula (I) and 1 to 10% by weight of a photosensitive binder resin.

It is needless to say that the colored photosensitive resin composition according to an embodiment of the present invention may further include at least one conventional additive selected from organic pigments, pigment dispersants, photoinitiators, photopolymerizable compounds, and solvents.

In one embodiment, the organic pigments may be used in combination of one or more of red, green, blue, yellow, purple pigments and the like, and as a non-limiting example thereof, C.I. Pigment Red 7, 14, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 117, 129, 138, 139, 146, 150, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272; C.I. Green pigments such as Pigment Green 7, 10, 36, 37 and 58; C.I. Blue pigments such as Pigment Blue 15: 1,15: 2,15: 3,15: 4,15: 6,16,80; C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 169, 170, 171, 172, 173, 193, 194, 199, 213 and 214; And C.I. Violet pigments such as Pigment Violet 23, 34, 35, and 37; And the like.

At this time, in view of realizing high transparency and color sharpness, the compound of the formula (1) can be used alone as a yellow pigment or as a mixed pigment mixed with one or more pigments selected from the above-mentioned green pigment and yellow pigment , And more particularly, as a mixed pigment mixed with one or more pigments selected from the above-mentioned green pigments.

The amount of the organic pigment to be used is not limited, but may be 0.1 to 20% by weight, specifically 0.1 to 10% by weight, more specifically 1 to 10% by weight based on the total weight of the composition.

The organic pigment may have a volume average particle diameter of 10 to 150 nm, specifically 30 to 110 nm, more specifically 40 to 80 nm.

In addition, the colored photosensitive resin composition according to an embodiment of the present invention may be included in the form of the above-described pigment dispersion. When the compound of Formula 1 is contained in the colored photosensitive resin composition in the form of a pigment dispersion, it may be contained in an amount of 0.01 to 20% by weight based on the solid content, but is not limited thereto.

The pigment dispersant may be added to maintain deaggregation and dispersion stability, and examples thereof include a resin type dispersant and a surfactant type dispersant.

In one embodiment, the resinous dispersant is selected from the group consisting of polyurethane; Polyester; Unsaturated polyamides; Phosphate esters; Polycarboxylic acids and their amine salts, ammonium salts, alkylamine salts; Polycarboxylic acid esters; Hydroxyl group-containing polycarboxylic acid esters; Polysiloxanes; Modified polyacrylates; Alginic acid, polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyvinylpyrrolidone, and gum arabic; Styrene-maleic acid ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, isobutylene, styrene-acrylic acid resin, styrene-acrylic acid- - ethylenic double bond-containing resins such as maleic acid resin, vinyl-ester resin and rosin-modified maleic acid resin; And amine-based resins such as polyallylamine, polyvinylamine, and polyethyleneimine; But is not limited thereto. Non-limiting examples of the resinous dispersant include BYK-Chemie Disperbyk-160, Disperbyk-161, Disperbyk-165, Disperbyk-168, Disperbyk-170, LPN-22131, LPN-22102, LPN-6919, LPN-22251, LPN-22822, LPN-22900, LPN-22238, LPN-22238, Dispervix- 21715 and LPN-22474; EFKA-4046, EFKA-4047 and EFKA-4340 from EFKA; Solsperse-5000, Solpus-12000, Solpus-22000, Solpus-24000 and Solpus-32500 from AVECIA; And PB-821, PB-822, PB-824 and PB-827 from AJINOMOTO; And the like.

At this time, the molecular weight of the resinous dispersant is not particularly limited, but may be a weight average molecular weight of 1,000 to 100,000 (measured by GPC method, in terms of polystyrene).

In one specific example, non-limiting examples of the surfactant type dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamines surfactants, fluorine surfactants, and fluorine surfactants. It is not limited.

The amount of the pigment dispersant to be used is not limited, but may be 0.01 to 20% by weight based on the total weight of the composition, and may be used in various combinations for achieving a desired viscosity. At this time, the amount of the pigment dispersant is preferably 1 to 20 wt%, more specifically 1 to 10 wt%.

In one embodiment, the photoinitiator may be at least one selected from an iodine salt compound, a sulfonium salt compound, a triazine compound, an oxime compound, and the like. Nonlimiting examples thereof include 2,4-bis (trichloromethyl) -6- Methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- -Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, -Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethyl Amino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] Triazine compounds such as 3,5-triazine; N -benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N -benzoyloxy- N -benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N -acetoxy- 1- [ -9 H -carbazol-3-yl] ethan-1-imine, N -acetoxy-1- [ oxa-bicyclo fentanyl methyloxy) benzoyl} -9 H - carbazole-3-yl] ethane-1-imine, N - acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9 H - carboxylic carbazole-3-yl] -3-cyclopentyl-propan-1-imine and N - benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) - H - carbazole-3-yl] -3 Oxime compounds such as cyclopentylpropan-1-one-2-imine; And Irgacure-907, 369, 379, Irgacure OXE-01 and Irgacure OXE-02 from BASF; And the like. In this case, specifically, N -benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -benzoyloxy- Imine and N -benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine; N -benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one, which is commercially available from commercial products such as Irgacure-907, 369 and 379 of BASF. More specifically, -N-2-imine, but is not limited thereto.

The photoinitiator may be used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and more preferably 0.5 to 3% by weight based on the total weight of the composition.

In one embodiment, the photopolymerizable compound is not limited as long as it has an unsaturated functional group, and non-limiting examples thereof include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethyl ethylphthalic acid , Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) Erythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. No.

The photopolymerizable compound may be present in an amount of 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight based on the total weight of the composition.

In one embodiment, the solvent is exemplified by the solvent included in the pigment dispersion, and the amount of the solvent to be used is not limited and is included as the remaining amount in the total weight of the composition.

The colored photosensitive resin composition according to one embodiment of the present invention has excellent transparency and tinting power and can be very usefully used for manufacturing a color filter for high color reproduction of low power.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

(Assessment Methods)

1. Heat resistance

The heat resistance evaluations for the compounds of Examples 1 to 11 and Comparative Example 1 were carried out using a thermogravimetric analyzer (Thermogravimetric Analyzer Q5000 Model, TA Instruments, TA Instruments). Table 5 shows the results of weight loss (%) at 230 ° C in accordance with LCD process conditions.

2. Chromaticity

For the evaluation of the luminance, the colored photosensitive resin compositions prepared in the following Examples 12 to 17 were each formed into a film using a spin coater and then dried in an oven at 80 ° C for 10 minutes to obtain a coating film. Then, the coating film was exposed using an ultra-high pressure mercury lamp at a light quantity of 100 mJ / cm ² , and was irradiated with a 0.04% KOH developer (containing 0.12 wt% of surfactant: Megapack F477 (Dainippon Ink and Chemical) For 60 seconds and then washed with ultrapure water. The developed coating film was thermally cured in an oven at 230 ° C for 20 minutes to prepare a film substrate having a color filter pattern.

Each of the film substrates manufactured by the above method was subjected to spectroscopic measurement with an MCPD-3000 colorimeter (manufactured by Ohtsuka Co., Ltd.), and the xy chromaticity coordinates (x, y = 0.567) in the XYZ color system of CIE using the characteristic function of the C light source, And Y were measured. The results are shown in Table 6 below.

(Example 1)

30.6 g (0.22 mol) of 2-nitrophenol (4) was dissolved in 500 ml of DMF, and 31.8 g (0.23 mol) of potassium carbonate and 20.7 g (0.11 mol) of dibromoethane were added thereto. The mixture was heated and stirred for 12 hours. Then, the reaction product was cooled to room temperature, and 1.5 L of distilled water was added thereto. After stirring for 1 hour, the product was filtered and sufficiently washed with distilled water. The obtained solid product was dispersed in 500 ml of methanol, stirred at room temperature for 30 minutes, filtered and dried to obtain 17.2 g (51.4%) of 1, 2-bis [2-nitrophenoxy] ethane (5).

10 g (33 mmol) of 1, 2-bis [2-nitrophenoxy] ethane (5) was dissolved in 60 ml of DMF, and hydrogen gas was added thereto with 0.5 g of a 10% Pd / C catalyst The reaction solution was heated to 70 to 80 캜 and reacted for 20 hours. Then, the reaction product was cooled to room temperature and filtered to remove the catalyst. 400 ml of distilled water was added to the reaction mixture, and the mixture was stirred for 1 hour. The product was filtered, washed sufficiently with distilled water and dried to obtain 1,2- Phenoxy] ethane (2) (7.7 g, 95.6%).

Step 2.

5.0 g (18.8 mmol) of 4- [5- ( t -butyl) benzooxazol-2-yl] aniline 6 was dissolved in 50 ml of toluene and the reaction solution was maintained at 5 캜, mmol) was slowly added over 30 minutes, and the reaction mixture was stirred at 5 ° C for 2 hours. Then, 2 ml of acetic acid was added thereto, and the reaction solution was heated to 65-70 ° C and stirred for 2 hours. Then, the reaction product was cooled to room temperature, and the obtained solid product was filtered, washed with 20 ml of toluene and dried to obtain N -4- [2-phenyl-5- t- butyl] benzoxazolyl-1,3-oxo-butanamide (3) (5.0 g, 76%).

Step 3.

1.0 g (4.1 mmol) of 1, 2-bis- [2-aminophenoxy] ethane (2) was dispersed in 10 ml of a 5 N hydrochloric acid aqueous solution and stirred at room temperature for 2 hours. Then, 7 g of ice was added to the reaction solution The reaction was cooled to 0-5 < 0 > C. Then 3 N sodium nitrite (NaNO ₂ ) 2.9 ml (8.7 mmol) was slowly added to the reaction mixture for 20 minutes while care was taken so that the temperature of the reaction did not exceed 5 ° C. The reaction mixture was stirred at 0-5 ° C for 1.5 hours, then 0.1 g of sulfamic acid was added to remove excess nitrite The diazotization reaction was completed.

2.87 g (8.2 mmol) of N -4- [2-phenyl-5- t -butyl] benzoxazolyl-1,3-oxo-butanamide 3 was dispersed in 15 ml of H ₂ O, And 0.1 g of dispersant were added in succession to completely dissolve the coupler. Then, the pH of the reaction solution was adjusted to 6 to 7 with 10% aqueous acetic acid solution, and the mixture was maintained at 0 to 5 ° C. Then, the diazotization solution obtained above was added slowly while being carefully controlled so that the temperature of the reaction did not rise. After stirring at 0 to 5 ° C for 1.5 hours, the reaction product was neutralized to pH = 6-7 with a saturated sodium carbonate aqueous solution, After stirring at 80 ° C for 1 hour, the reaction product was filtered at high temperature. The obtained solid product was dispersed in 100 ml of ethanol and stirred at room temperature for 30 minutes, followed by filtration and drying to obtain 2, 2- [1, 2-ethanediylbis (oxy- diyl)] bis [N - (2, 3- dihydro-2-oxo -1 H - (2- phenyl -5- t - butyl) benzoxazolyl-6-yl) -3-oxo-butane amide (1 ) 3.1 g (78.3%).

Table 1 shows the mass spectra (MS, m / e ) and ¹ H NMR spectrum data of the structures and intermediates of Example 1.

(Examples 2 to 3)

Synthesis of a bis-nitrophenoxyethane derivative of Compound 7 and Compound 9 using the following phenol derivative as a starting material was carried out in the same manner as in Step 1 of Example 1, and a reduction reaction was carried out to obtain a bisaminophenoxy Synthesis of Siethane derivatives is shown in Table 2 below.

Table 2 shows the structural formulas, amounts and synthesis yields of phenol derivatives, bisnitrophenoxyethane derivatives and bisaminophenoxyethane derivatives which are starting materials of Examples 2 to 3. Mass spectrum (MS, m / e ) and ¹ H NMR spectrum data showing the structures of intermediates and products are shown in Table 2 below.

(Examples 4 to 8)

The disazo yellow pigment was synthesized by reacting the bisaminophenoxyethane derivative and the acetoacetanilide derivative shown in Table 3 below in the same manner as in Example 1, and the results are shown in Table 3 below.

Table 3 below shows the structural formulas, amounts and synthesis yields of the bisaminophenoxyethane derivatives and acetoacetanilide derivatives of Examples 4 to 8.

In addition, mass spectrum (MS, m / e ) and ¹ H NMR spectrum data of the structure of Compound 11 are shown in Table 3 below.

(Examples 9 to 11)

The disazo yellow pigment was synthesized by reacting a bisaminophenoxyethane derivative and a pyridone derivative as shown in the following Table 4 in the same manner as in Example 1,

Table 4 below shows the structural formulas, amounts and synthesis yields of the bisaminophenoxyethane derivatives and pyridone derivatives of Examples 9 to 11.

Table 5 also shows the mass spectra (MS (FAB), m / e ], elemental analysis (EA) and heat resistance evaluation (TGA) results of the disazo yellow pigments of Example 1 and Examples 4 to 11 .

As shown in Table 5, it can be seen that the disazo yellow pigment of the examples is excellent in heat resistance. Particularly, in the case of the disazo yellow pigment of Example 1, it has remarkably improved heat resistance as compared with P. Y.180, which is one of typical disazo yellow pigments used for coloring color materials for color filters.

(Example 12)

, 3.0 wt% of Pigment Green 58 (PG 58), 1.8 wt% of Pigment Yellow 138 (PY 138), 0.2 wt% of the disazo yellow pigment (Compound 1) prepared in Example 1, a resinous dispersant 2.0% by weight based on the solids content of DISPERBIC-21116 (BYK-KEMISA), 3.0% by weight of SPCG-19X (Showa Denko) (acid value of 110 KOH mg / g, Mw = 10,000) as a photosensitive binder resin, 30.0% by weight of glycol monomethyl ether acetate (PGMEA) and 15.0% by weight of diacetone alcohol were mixed and dispersed with a bead mill and then dispersed in a photosensitive bead mill SPCG-19X (Showa Denko) , 1.5% by weight of Irgacure-369 (BASF) as a photoinitiator, 7.0% by weight of dipentaerythritol hexaacrylate as a photopolymerizable compound, and 0.5% by weight of a surfactant-type dispersant 0.01% by weight of LOMEGA Pack F477 (Dainippon Ink and Chemicals) , PGMEA was stirred to give 25.49% by weight is applied to the adding and diacetone alcohol 10.0% by weight to obtain a colored photosensitive resin composition of the green.

The chromaticity of the film substrate produced using the green colored photosensitive resin composition was evaluated.

(Examples 13 to 17)

A green colored photosensitive resin composition was obtained in the same manner as in Example 12 except that each of the pigment combinations in Table 6 was used.

The chromaticity of the film substrate produced using each colored photosensitive resin composition was also evaluated.

As shown in Table 6, it was confirmed that the colored photosensitive resin composition employing the yellow pigment of the Examples does not cause deterioration of transparency and tinting power even during the high temperature process, and thus it is possible to realize a clear color. In particular, it has been confirmed that the colored photosensitive resin composition can realize high reproducibility in the implementation of color.

In addition, the colored photosensitive resin composition employing the yellow pigment of the embodiment can be dispersed with excellent dispersibility to improve storage stability, and can provide a color filter having a high luminance and a high contrast ratio by realizing bright colors.

In addition, the colored photosensitive resin composition employing the yellow pigment of the examples can provide a high-quality color filter with less change in transparency even after thermal curing and ensuring thermal stability and light stability.

Therefore, the compound according to one embodiment of the present invention provides a color filter having excellent optical properties, which is used as a yellow pigment for use as a color filter requiring a high-temperature process as well as a coloring agent such as printing ink, paint and plastic It is expected to be possible.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. .

Claims (12)

delete A compound represented by the following formula (2):
(2)

[In the formula (2)
R ₁₁ and R ₁₃ are independently selected from halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy, C ₁ -C ₂₀ alkyl, halo C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ each Aryl or C ₆ -C ₂₀ heteroaryl;
R ₁₂ and R ₁₄ are each independently hydrogen, halo, hydroxy, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, hydroxy C ₁ -C ₂₀ alkyl or halo C ₁ -C ₂₀ alkyl;
L ₁ and L ₂ are each independently a direct bond, C ₆ -C ₂₀ arylene or C ₆ -C ₂₀ heteroarylene;
Wherein said heteroarylene and heteroaryl comprise at least one member selected from B, N, O, S, Se, -P (= O) -, -C (= O) 3. The method of claim 2,
In Formula 2, L ₁ and L ₂ are each independently a direct bond or C ₆ -C ₁₂ arylene. delete delete delete 3. The method of claim 2,
Lt; / RTI > is selected from the following structures.

A pigment dispersion comprising the compound of any one of claims 2, 3 and 7. 9. The method of claim 8,
Based on the total weight of the pigment dispersion,
0.01 to 20% by weight of said compound and a balance solvent. A colored photosensitive resin composition comprising the compound of any one of claims 2, 3, and 7 and a photosensitive binder resin. 11. The method of claim 10,
A colorant, an organic pigment, a pigment dispersant, a photoinitiator, a photopolymerizable compound and a solvent. A color filter comprising a colored layer formed by curing a colored photosensitive resin composition according to claim 10.