KR101711922B1 - Novel compound, photosensitive resin composition, and color fliter - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.) There is provided a compound represented by the following formula (1).
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, a photosensitive resin composition containing the compound, and a color filter (NOVEL COMPOUND, PHOTOSENSITIVE RESIN COMPOSITION, AND COLOR FLITER)

The present invention relates to a novel compound, a photosensitive resin composition containing the compound, and a color filter.

In a color filter made of a pigment type photosensitive resin composition, there is a limit of luminance and contrast ratio resulting from the pigment particle size. Further, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required for forming a fine pattern. In order to meet such a demand, attempts have been made to fabricate a photosensitive resin composition in which a dye that does not form particles is introduced instead of a pigment, thereby realizing a color filter having improved color characteristics such as brightness and contrast ratio.

Therefore, it is necessary to study a compound suitable as a dye used in the production of a photosensitive resin composition.

One embodiment of the present invention is directed to providing novel compounds.

Another embodiment of the present invention is to provide a photosensitive resin composition comprising the compound.

Another embodiment of the present invention is to provide a color filter manufactured using the photosensitive resin composition.

An embodiment of the present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ to R ¹³ are each independently a hydrogen atom, a halogen atom, or a group represented by the following formula (2)

At least one of R ¹ to R ⁸ is represented by the following formula (2)

(2)

In Formula 2,

R ¹⁴ represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group to be.

In Formula 2, "substituted" to "substituted" means one or more hydrogen atom is a nitro group, a cyano group, an amino group of a functional group ^{_{(NH 2, NH (R 200}} ), or ^{N (R 201) (R 202} ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are each independently a C1 to C10 alkyl group), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, or a C6 to C12 aryl group it means.

At least one of R ¹ to R ⁴ and at least one of R ⁵ to R ⁸ may be represented by the formula (2).

At least one of R ¹ to R ⁴ is represented by the general formula (2) and all others are halogen atoms, at least one of R ⁵ to R ⁸ is represented by the general formula (2) ⁹ to R ¹³ may all be hydrogen atoms.

The halogen atom may be a fluorine atom or a chlorine atom.

 The compound may have a solubility of 10 g / 100 g of propylene glycol monomethyl ether acetate to 30 g / 100 g of propylene glycol monomethyl ether acetate at 25 ° C to 50 ° C.

The compound represented by the formula (1) may be represented by any one of the following formulas (3) to (8).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

The compound represented by Formula 1 may be a dye, for example, a yellow dye compound.

Another embodiment of the present invention provides a photosensitive resin composition comprising the compound.

The photosensitive resin composition may include a compound according to one embodiment, a binder resin, a pigment, and a solvent.

The photosensitive resin composition may further comprise a photopolymerizable compound and a photopolymerization initiator.

Another embodiment of the present invention provides a color filter manufactured using the photosensitive resin composition.

The compound according to one embodiment of the present invention exhibits excellent yellow spectral characteristics by having a modified thiol group, and thus can be used as a dye in the production of a photosensitive resin composition for a color filter, for example, a photosensitive resin composition for a yellow color filter, May have excellent brightness and contrast ratio.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group and NH _2, NH (R ^200), or N (R ²⁰¹⁾ (R ^202), wherein R ^200, R ^201, and R ²⁰² are the same or different, each independently being a C1 to C10 alkyl group), an amidino A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, "alkyl group" means C1 to C20 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C20 cycloalkyl group, specifically C3 Refers to a C1 to C20 alkoxy group, specifically, a C1 to C18 alkoxy group, and an "aryl group" means a C6 to C20 aryl group, specifically, a C6 to C20 aryl group, Refers to a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" refers to a C 1 to C 20 alkylene group, specifically, a C1 Refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

Unless otherwise specified in the present specification, the term "aliphatic organic group" means a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkylene group, a C2 to C20 alkenylene group, Means a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, Means a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C3 to C20 cycloalkylene group, a C3 to C20 cycloalkenylene group, or a C3 to C20 cycloalkynylene group. C3 to C15 cycloalkenyl groups, C3 to C15 cycloalkynyl groups, C3 to C15 cycloalkylene groups, C3 to C15 cycloalkenylene groups, Or an aromatic organic group means a C6 to C20 aryl group or a C6 to C20 arylene group, specifically a C6 to C16 aryl group or a C6 to C16 arylene group, The "heterocyclic group" means a C2 to C20 cycloalkyl group containing 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si and combinations thereof in one ring, C2 to C20 cycloalkyl Means a C2 to C20 cycloalkenyl group, a C2 to C20 cycloalkenylene group, a C2 to C20 cycloalkynyl group, a C2 to C20 cycloalkynylene group, a C2 to C20 heteroaryl group, or a C2 to C20 heteroarylene group, Specifically, C2 to C15 cycloalkyl groups containing 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring, C2 to C15 A C2 to C15 cycloalkenyl group, a C2 to C15 cycloalkynylene group, a C2 to C15 cycloalkynylene group, a C2 to C15 heteroaryl group, or a C2 to C15 heteroarylene group, it means.

As used herein, unless otherwise defined, "combination" means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

An embodiment provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ to R ¹³ are each independently a hydrogen atom, a halogen atom, or a group represented by the following formula (2)

At least one of R ¹ to R ⁸ is represented by the following formula (2)

(2)

In Formula 2,

R ¹⁴ represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group to be.

(In the formula 2, "substituted" to "substituted" means one or more hydrogen atom is a nitro group, a cyano group, an amino group of a functional group (NH _2, NH (R ^200), or ^{N (R 201) (R 202} ), (Wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are each independently a C 1 to C 10 alkyl group), a C 1 to C 10 alkyl group, a C 1 to C 10 alkoxy group, or a C 6 to C 12 aryl group. .)

In the case of the compound represented by the above formula (1), at least one of R ¹ to R ⁸ is represented by the above formula (2), thereby exhibiting excellent yellow spectral characteristics and exhibiting a clearer color even in a small amount, . Further, the color filter using the compound represented by the above formula (1) as a dye has excellent brightness and contrast ratio.

In general, dyes are the most expensive component of the components used in color filters. Therefore, in order to achieve a desired effect, for example, a high luminance and a high contrast ratio, it is necessary to use more expensive dye, so that the production cost has to be increased. However, when the compound according to one embodiment is used as a dye in a color filter, excellent color characteristics such as high luminance and high contrast ratio can be achieved even in a small amount, so that production cost can be reduced.

 In addition, although the pigment has a problem of poor stability due to its low solubility in an organic solvent, the compound can be dissolved in an amount of 10 g to 30 g per 100 g of propylene glycol monomethyl ether acetate (PGMEA) at a temperature of 25 ° C to 50 ° C. That is, the compound may have a solubility of 100 g / g of propylene glycol monomethyl ether acetate (PGMEA) to 100 g / g of propylene glycol monomethyl ether acetate (PGMEA) at a temperature of 25 ° C to 50 ° C, The brightness and contrast ratio can be improved.

For example, at least one of R ¹ to R ⁴ and at least one of R ⁵ to R ⁸ may be represented by the formula (2).

For example, at least one of R ¹ to R ⁴ is represented by the general formula (2) and all others are halogen atoms, at least one of R ⁵ to R ⁸ is represented by the general formula (2) R ⁹ to R ¹³ may all be hydrogen atoms.

For example, the compound may be represented by any one of the following Chemical Formulas (3) to (8).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

According to another embodiment, there is provided a photosensitive resin composition comprising the compound according to one embodiment.

For example, the photosensitive resin composition includes a compound according to one embodiment, a binder resin, a pigment, and a solvent.

The compound according to one embodiment may function as a colorant, for example, a dye to exhibit excellent color characteristics.

For example, the pigment may be a yellow pigment.

The yellow pigments have a C.I. Pigment yellow 139, C.I. Pigment yellow 138, C.I. Pigment yellow 150, and the like. These may be used singly or in combination of two or more, but the present invention is not limited thereto.

The pigment may be contained in the photosensitive resin composition in the form of a pigment dispersion, and the pigment may be included in an amount of 1% by weight to 30% by weight based on the total amount of the photosensitive resin composition.

In addition, the pigment dispersion may further include a dispersant. As the dispersing agent, nonionic, anionic or cationic dispersing agents can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts , A sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine. These dispersants may be used singly or in combination of two or more.

The dispersing agent may be contained in an amount of 0.01 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, so that excellent stability, developability and patternability can be obtained.

The photosensitive resin composition may be prepared by mixing a dye and a pigment in a weight ratio of 1: 9 to 5: 5, for example, in a weight ratio of 3: 7 to 5: 5. When they are mixed in the weight ratio range, a high contrast ratio can be obtained while maintaining color characteristics.

The compound according to one embodiment may be included in an amount of 0.1% by weight to 30% by weight based on the total amount of the photosensitive resin composition.

The binder resin may be an acrylic resin.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and may be a resin containing at least one acrylic repeating unit.

The acrylic resin may be a copolymer of the second ethylenically unsaturated monomer.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin include (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2- Acrylate copolymer, a (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and a benzyl methacrylate copolymer. However, it is not limited to these, More than two species may be used in combination.

The weight average molecular weight of the binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition for a color filter has excellent physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate in the production of a color filter.

The acid value of the binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 20 mgKOH / g to 50 mgKOH / g. When the acid value of the binder resin is within the above range, the resolution of the pixel pattern is excellent.

The binder resin may be contained in an amount of 1 wt% to 40 wt%, for example, 1 wt% to 20 wt% based on the total amount of the photosensitive resin composition for a color filter. When the alkali-soluble resin is contained within the above-mentioned range, the color filter is excellent in developing property and the crosslinking property is improved, so that excellent surface smoothness can be obtained.

The solvent may be a compound having compatibility with a compound according to one embodiment, a binder resin, a pigment, a dispersing agent and the like but not reacting.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in a residual amount, for example, from 40% by weight to 90% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the color filter is excellent.

The photosensitive resin composition may further comprise a photopolymerizable compound and a photopolymerization initiator in addition to a binder resin, a pigment, a dispersant, and a solvent.

The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.

Examples of commercially available products of photopolymerizable compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable compound may be treated with an acid anhydride to give better developing properties.

The photopolymerizable compound may be contained in an amount of 1 to 15% by weight, for example, 5 to 10% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above-mentioned range, the pattern forming process sufficiently cures upon exposure to light, which is excellent in reliability and developability in an alkaline developer.

The photopolymerization initiator may be, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an oxime-based compound or a combination thereof as an initiator generally used in a photosensitive resin composition.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O- Acetate and the like.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be contained in an amount of 0.01 wt% to 10 wt%, for example, 0.1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

The photosensitive resin composition according to another embodiment may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be contained in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the above range, the adhesiveness and storage stability are excellent.

The photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group in order to improve the adhesion with the substrate.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the adhesion and storage stability are excellent.

The above-mentioned photosensitive resin composition may further contain a surfactant for improving coatability and preventing defect formation if necessary.

Examples of the surfactants include, BM Chemie BM-1000 ^® of社, BM-1100 ^®, and the like; Mechacup F 142D ^® , copper F 172 ^® , copper F 173 ^® , copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray silicone (Note)社SH-28PA ^®, copper -190 ^®, may be used copper ^® -193, fluorine-based surfactants and commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting of the glass substrate is excellent.

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

According to another embodiment, there is provided a color filter manufactured using the photosensitive resin composition according to the above embodiment.

The pattern forming process in the color filter is as follows.

Applying the photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film; Developing the exposed photosensitive resin composition film with an aqueous alkali solution to produce a photosensitive resin film; And a step of heat-treating the photosensitive resin film. The process conditions and the like are well known in the art, and therefore, detailed description thereof will be omitted herein.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.

(Synthesis of Compound)

Synthetic example  1: Synthesis of Compound Represented by Formula 3

1.3 g of a compound represented by the following formula A, 3.0 ml of butanethiol, 55 ml of acetone and 5.0 g of K ₂ CO ₃ were added to a 250 ml flask and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following general formula (3).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.88 (d, J = 2.2 Hz, 1H), 7.22-7.18 (m, 2H), 7.10 (d, J = 2.2 Hz, 1H), 6.83 (m, 1H), 5.78 (s, 1H), 2.77 (t, J = 6.8 Hz, 4H), 1.63 (m, 4H), 1.33 (m, 4H), 0.93 (t, J = 6.8 Hz, 6H) ppm; HRMS (ESI-TOF) = 801

MS  data

(M @ ⁺ ); Anal. Calcd for C ₃₄ H ₂₄ C ₁₆ N ₂ O ₄ S ₂ : C, 50.96; H, 3.02; N, 3.50; S, 8.00. Found: C, 50.87; H, 3.37; N, 3.33; S, 8.16.

(A)

(3)

Synthetic example  2: Synthesis of Compound Represented by Formula 4

1.3 g of the compound represented by the above formula (A), 3.0 ml of isobutyl mercaptan, 55 ml of acetone and 5.0 g of K ₂ CO ₃ were added to a 250 ml flask and reacted by stirring at room temperature for 24 hours. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and vacuum dried to obtain a compound represented by the following general formula (4).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.82 (d, J = 2.1 Hz, 1H), 7.23-7.19 (m, 2H), 7.11 (d, J = 2.1 Hz, 1H), 6.84 (m, 1H), 5.77 (s, 1H), 2.73 (dd, J = 9.2, 5.4 Hz, 4H), 2.11 (m, 4H), 1.01 (d, J = 6.8 Hz, 12H) ppm; HRMS (ESI-TOF) = 801

MS  data

(M @ ⁺ ); Anal. Calcd for C ₃₄ H ₂₄ C ₁₆ N ₂ O ₄ S ₂ : C, 50.96; H, 3.02; N, 3.50; S, 8.00. Found: C, 50.65; H, 3.23; N, 3.41; S, 8.46.

[Chemical Formula 4]

Synthetic example  3: Synthesis of Compound Represented by Formula 5

1.3 g of the compound represented by the above formula A, 3.0 ml of 2-propane thiol, 55 ml of acetone and 5.0 g of K ₂ CO ₃ were added to a 250 ml flask, and the mixture was reacted for 24 hours at room temperature with stirring. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following formula (5).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.84 (d, J = 2.2 Hz, 1H), 7.23-7.19 (m, 2H), 7.11 (d, J = 2.2 Hz, 1H), 6.84 (m, 1H), 5.77 (s, 1H), 2.73 (dd, J = 9.2, 5.4 Hz, 4H), 2.88 (m, 4H), 1.27 (d, J = 6.8 Hz, 12H) ppm; HRMS (ESI-TOF) = 773

MS  data

(M @ ⁺ ); Anal. _{Calcd for C 32 H 20 C l6} N 2 O 4 S 2: C, 49.70; H, 2.61; N, 3.62; S, 8.29. Found: C, 49.55; H, 3.48; N, 3.44; S, 8.10.

[Chemical Formula 5]

Synthetic example  4: Synthesis of Compound Represented by Formula 6

1.3 g of the compound represented by the above formula (A), 3.0 ml of cyclopentane thiol, 55 ml of acetone and 5.0 g of K ₂ CO ₃ were added to a 250 ml flask, and the mixture was reacted by stirring at room temperature for 24 hours. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following formula (6).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.82 (d, J = 2.0 Hz, 1H), 7.23-7.19 (m, 2H), 7.11 (d, J = 2.0 Hz, 1H), 6.82 (m, 1H), 5.78 (s, 1H), 2.57-2.54 (m, 4H), 1.95-1.92 (m, 4H), 1.70-1.45 (m, 12H) ppm; HRMS (ESI-TOF) = 825

MS  data

(M @ ⁺ ); Anal. Calcd for C ₃₆ H ₂₄ C ₁₆ N ₂ O ₄ S ₂ : C, 52.38; H, 2.93; N, 3.39; S, 7.77. Found: C, 52.42; H, 2.84; N, 3.41; S, 8.01.

[Chemical Formula 6]

Synthetic example  5: Synthesis of the compound represented by the formula (7)

1.3 g of the compound represented by the above formula A, 3.0 ml of benzenethiol, 55 ml of acetone and 5.0 g of K ₂ CO ₃ were added to a 250 ml flask, and the mixture was reacted for 24 hours at room temperature with stirring. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following general formula (7).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.82 (d, J = 2.0 Hz, 1H), 7.23-7.19 (m, 6H), 7.09-7.00 (m, 7H), 6.83 (m, 1H), 5.78 (s, 1H), 2.57-2.54 (m, 4H), 1.95-1.92 (m, 4H), 1.70-1.45 (m, 12H) ppm; HRMS (ESI-TOF) = 841

MS  data

(M @ ⁺ ); Anal. Calcd for C ₃₈ H ₁₆ C ₁₆ N ₂ O ₄ S ₂ : C, 54.24; H, 1.92; N, 3.33; S, 7.62. Found: C, 54.42; H, 1.83; N, 3.19; S, 7.83.

(7)

Synthetic example  6: Synthesis of Compound Represented by Formula 8

Into a 250 mL flask were added 1.3 g of the compound represented by the above formula A, 3.0 mL of benzyl mercaptan, 55 mL of acetone and 5.0 g of K ₂ CO ₃ , and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following general formula (8).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.82 (d, J = 2.0 Hz, 1H), 7.21-7.05 (m, 13H), 6.83 (m, 1H), 5.78 (s, 1H), 4.03 (s, 4H) ppm; HRMS (ESI-TOF) = 869

MS  data

(M @ ⁺ ); Anal. _{Calcd for C 40 H 20 C l6} N 2 O 4 S 2: C, 55.26; H, 2.32; N, 3.22; S, 7.38. Found: C, 55.14; H, 2.38; N, 3.10; S, 7.54.

[Chemical Formula 8]

compare Synthetic example  1: Synthesis of Compound Represented by Formula 9

To a 250 mL flask was added 1.0 g of yellow dye 139, 3.0 mL of bromo butane, 55 mL of acetone and 5.0 g of K ₂ CO ₃ , and the mixture was reacted for 24 hours at room temperature with stirring. After completion of the reaction, the solvent was removed by filtration. Dichloromethane was appropriately added to the obtained solid to dissolve the solid, and hexane was added to crystallize it. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following general formula (9).

^One H NMR  data

^{1 H NMR (400 MHz, DMSO} ) 7.25 (m, 2H), 7.09 (m, 2H), 4.12 (br, s 1H), 3.16 (t, J = 6.8 Hz, 8H), 1.55 (m, 8H), 1.33 (m, 8 H), 0.94 (t, J = 6.8 Hz, 12 H) ppm; HRMS (ESI-TOF) = 591

MS  data

(M @ ⁺ ); Anal. _{Calcd for C 32 H 41 N 5} O 6: C, 64.96; H, 6.98; N, 11.84. Found: C, 64.77; H, 7.03; N, 11.75.

[Chemical Formula 9]

(Synthesis of photosensitive resin composition)

Example  1 to 6 and Comparative Example  1 to 4

The photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by mixing the following components in the compositions shown in Table 1 below.

(Unit: wt%) ingredient content Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 dyes A 6.5 - - - - - - - - - B - 6.5 - - - - - - - - C - - 6.5 - - - - - - - D - - - 6.5 - - - - - - E - - - - 6.5 - - - - - F - - - - - 6.5 - - - - G - - - - - - - - - 19.5 Pigment A 13.0 13.0 13.0 13.0 13.0 13.0 19.5 13.0 10.4 - B - - - - - - - 6.5 9.1 - Binder resin 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 Dispersant 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 menstruum 71.4 71.4 71.4 71.4 71.4 71.4 71.4 71.4 71.4 71.4

In Table 1, the components used in the synthesis of the photosensitive resin composition are as follows.

(dyes)

  Dye A: Compound represented by the general formula (3)

  Dye B: Compound represented by formula (4)

  Dye C: Compound represented by the general formula (5)

  Dye D: A compound represented by the formula (6)

  Dye E: Compound represented by the general formula (7)

  Dye F: Compound represented by the formula (8)

  Dye G: Compound represented by the formula (9)

(Pigment)

  Pigment A: Yellow pigment 138 (Sanyo, Y138)

  Pigment A: Yellow pigment 150 (Sanyo, Y150)

(Binder resin)

  Methacrylic acid / benzyl methacrylate copolymer (available from Mi-won Co., NPR1520)

(Dispersant)

  BYK-301 (BYK Chem)

(menstruum)

Propylene glycol methyl ethyl acetate (Shiny)

Evaluation 1: Measurement of solubility

The solubilities of the compounds represented by the above formulas (3) to (9), yellow pigment (138), and yellow pigment (150) in PGMEA (100 g) were measured and the results are shown in Table 2 below.

(Unit: g) compound Solubility (3) 19.2 Formula 4 18.5 Formula 5 17.1 6 15.7 Formula 7 13.0 8 12.5 Formula 9 10.1 Yellow pigment 138 Less than 1.0 Yellow pigment 150 Less than 1.0

From the above Table 2, it can be seen that the compounds (Formulas 3 to 8) according to one embodiment have higher solubility in an organic solvent than the compound represented by Formula 9 and the pigment, and the photosensitive resin composition using the compound according to one embodiment as a dye, It can be confirmed that excellent stability can be obtained.

Evaluation 2: Color coordinates , Luminance, contrast ratio measurement

The photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 4 was coated on a 1 mm thick glass substrate having a thickness of 1 to 3 占 퐉 and washed on a hot plate at 90 占 폚 for 2 minutes Lt; / RTI > to obtain a coating film. Subsequently, a coating film was obtained by exposure using a high-pressure mercury lamp having a dominant wavelength of 365 nm. And dried in a hot air circulating drying oven at 200 ° C for 5 minutes. The color layers (x, y), luminance (Y), and contrast ratio were measured using a spectrophotometer (MCPD3000, Otsuka electronic Co.)

x y Luminance (Y) Contrast ratio Example 1 0.279 0.560 62.9 14,570 Example 2 0.278 0.560 63.1 14,680 Example 3 0.274 0.560 62.5 14,300 Example 4 0.272 0.560 61.2 14,830 Example 5 0.271 0.560 61.0 14,500 Example 6 0.270 0.560 59.9 14,200 Comparative Example 1 0.273 0.560 59.0 13,200 Comparative Example 2 0.269 0.560 58.4 12,700 Comparative Example 3 0.271 0.560 57.5 12,400 Comparative Example 4 0.265 0.560 56.5 12,200

From Table 3, it can be seen that the photosensitive resin compositions of Examples 1 to 6 containing the compound according to one embodiment as a dye show color characteristics superior to those of the photosensitive resin compositions of Comparative Examples 1 to 4, .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (10)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ¹ to R ¹³ are each independently a hydrogen atom, a halogen atom, or a group represented by the following formula (2)
At least one of R ¹ to R ⁸ is represented by the following formula (2)
(2)

In Formula 2,
R ¹⁴ is a hydrogen atom, an unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
Means that at least one hydrogen atom of the functional group is a nitro group, cyano group, amino group ((NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ) ²⁰⁰ , R ²⁰¹ , and R ²⁰² are the same or different from each other and are each independently a C1 to C10 alkyl group), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, or a C6 to C12 aryl group Substituted by a substituent.
The method according to claim 1,
At least one of R ¹ to R ⁴ and at least one of R ⁵ to R ⁸ is represented by the formula (2).
The method according to claim 1,
At least one of R ¹ to R ⁴ is represented by the general formula (2), and the others are all halogen atoms,
At least one of R ⁵ to R ⁸ is represented by the general formula (2), and all others are halogen atoms,
Wherein each of R ⁹ to R ¹³ is a hydrogen atom.
The method according to claim 1,
Wherein said compound is a dye.
5. The method of claim 4,
Wherein the dye is a yellow dye.
The method according to claim 1,
Wherein said compound has a solubility of 10 g to 30 g per 100 g of propylene glycol monomethyl ether acetate at a temperature of 25 캜 to 50 캜.
The method according to claim 1,
Wherein said compound is represented by any one of the following Chemical Formulas (3) to (8).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

A photosensitive resin composition comprising the compound of any one of claims 1 to 7.
9. The method of claim 8,
The photosensitive resin composition further comprises a binder resin, a pigment, and a solvent.
A color filter produced by using the photosensitive resin composition of claim 8.