KR101711921B1 - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant comprising a dye represented by the following formula (1); And (E) a solvent, and a color filter using the same.
[Chemical Formula 1]

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

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition and a color filter using the same.

Recently, as the spread of the large-screen liquid crystal display device has expanded, a demand for a new performance enhancement for the liquid crystal display device has been increasing. Among the components of the liquid crystal display device, the color filter is the most important color realizing device. Research is continuing. In addition, in the case of a liquid crystal display device having a large screen, the concentration of the colorant in the photosensitive resin composition is increased in manufacturing a color filter in order to increase color purity.

The color filter using the photosensitive resin composition can be produced by coating three or more kinds of hues on a transparent substrate mainly by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, etc. Recently, pigment dispersion technology has been improved and excellent color reproducibility Pigment dispersion method is widely used to ensure durability against heat, light and humidity.

However, in the case of the pigment dispersion method, for example, in order to form a red pixel which displays a region having a high coloring power (high concentration region) on a color coordinate system by using a red pigment, the content of the red pigment must be increased. In order to secure a high transmittance, there is a method of using a yellow pigment at a high concentration to shift color coordinates in the yellow direction. However, when the content of the yellow pigment is increased, the total content of the pigments is increased. Further, in a color filter made of a photosensitive resin composition containing a pigment, there is a limit in that the luminance and the contrast ratio are lowered due to the pigment particle size and the aggregation of the pigment particles.

In order to solve these limitations, research is underway to use a photosensitive resin composition which does not form particles or has a dye whose primary particle diameter is smaller than that of the pigment dispersion.

One embodiment is to provide a photosensitive resin composition excellent in tinting strength, heat resistance and chemical resistance.

Another embodiment is to provide a color filter using the photosensitive resin composition.

One embodiment includes (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant comprising a dye represented by the following formula (1); And (E) a solvent.

[Chemical Formula 1]

In Formula 1,

R ¹ to R ¹³ each independently represent 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, 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 .

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 the others may be a halogen atom,

At least one of R ⁵ to R ⁸ is represented by the general formula (2), and all of the other R ⁵ to R ⁸ may be a halogen atom,

R ⁹ to R ¹³ may all be hydrogen atoms.

The dye represented by Formula 1 may be a yellow dye.

The solubility of the dye represented by Formula 1 may be 10 g to 30 g per 100 g of propylene glycol monomethyl ether acetate (PGMEA) at a temperature of 25 ° C to 50 ° C.

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

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

The photosensitive resin composition may further comprise an antioxidant.

The antioxidant may be represented by the following general formula (9).

[Chemical Formula 9]

In the above formula (9)

L ¹ to L ⁸ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ¹⁷ to R ³⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,

At least one of R ¹⁷ to R ²¹ , at least one of R ²² to R ²⁶ , at least one of R ²⁷ to R ³¹ , and at least one of R ³² to R ³⁶ is a hydroxy group,

At least two of R ¹⁷ to R ²¹ , at least two of R ²² to R ²⁶ , at least two of R ²⁷ to R ³¹ , and at least two of R ³² to R ³⁶ are t-butyl groups.

Each of L ¹ to L ⁸ may independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The antioxidant may be represented by the following general formula (10).

[Chemical formula 10]

The antioxidant may be represented by the following general formula (11).

(11)

The antioxidant may be contained in an amount of 0.01% by weight to 1% by weight based on the total amount of the photosensitive resin composition.

The colorant may further comprise a pigment.

The pigment may be a green pigment, a yellow pigment or a combination thereof.

The dyes and pigments represented by Formula 1 may be contained in a weight ratio of 1: 9 to 9: 1.

Wherein the photosensitive resin composition comprises (A) 1 to 30% by weight of the binder resin, (B) 1 wt% to 20 wt% of the photopolymerizable monomer; (C) 0.1 to 10% by weight of the photopolymerization initiator; (D) 1% to 20% by weight of the colorant; And (E) the solvent balance.

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; And at least one additive selected from a radical polymerization initiator.

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

Other details of the embodiments of the present invention are included in the following detailed description.

The photosensitive resin composition is excellent in coloring power, heat resistance, and chemical resistance, and thus can be usefully used in color filters.

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

Unless otherwise noted herein, "substituted" is at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group ((NH _2, NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are each independently a Cl to C10 alkyl group), imino group, azido group, amidino group, hydrazino group A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a sulfonic acid group or a salt thereof, a hydrazino group, a carbonyl group, a carbamoyl group, a thiol group, C2 to C20 heterocycloalkyl groups, C2 to C20 heterocycloalkyl groups, C2 to C20 alkynyl groups, C1 to C20 alkoxy groups, C6 to C30 aryl groups, C3 to C20 cycloalkyl groups, C3 to C20 cycloalkenyl groups, C3 to C20 cycloalkynyl groups, An alkenyl group, a C2 to C20 heterocycle A C3 to C30 heteroaryl group, or a combination thereof.

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.

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

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

Also, unless otherwise specified in the present specification, "t-butyl group" means "tert-butyl group".

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

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 chemical formulas described herein, "*" means the same or different atom or moiety connected to the chemical formula.

The photosensitive resin composition according to one embodiment comprises (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant comprising a dye; And (E) a solvent.

The colorant (D) comprises a dye represented by the following formula (1), and the photosensitive resin composition contains the dye, thereby improving coloring power and further improving heat resistance and chemical resistance, thereby realizing excellent process characteristics.

[Chemical Formula 1]

In Formula 1,

R ¹ to R ¹³ each independently represent 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, 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 .

Each component will be described in detail below.

(D) Colorant

The colorant includes the dye represented by the formula (1).

In the case of the dye 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 in a small amount, . Furthermore, the color filter manufactured using the dye represented by Formula 1 has excellent brightness and contrast ratio.

In general, dyes are relatively expensive components among the components used in the color filter. Therefore, in order to achieve a desired effect, for example, high brightness and high contrast ratio, it is necessary to use more expensive dye, so that the production cost has to be increased. However, since the dye represented by the above formula (1) can achieve excellent color characteristics such as high luminance and high contrast ratio even in a small amount, the production cost can be reduced.

Unlike a pigment having a particle property, unlike a pigment having a particle property, a dye has no particle property in a solution state or has a very small primary particle size of 1 nm to 10 nm and is excellent in solubility in a solvent. When the particle diameter of the dye is very small Since the light scattering is reduced and consequently the contrast ratio and the luminance can be improved, it is possible to compensate the decrease of the contrast ratio and luminance, which are problems of the pigment dispersion method which is mainly used in the manufacture of color filters.

The dye represented by Formula 1 may 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 solubility of the dyes represented by the above formula (1) can be controlled by adjusting the solubility of the dye in the range of 10 g to 30 g / 100 g of propylene glycol monomethyl ether acetate (PGMEA) such as 10 g to 20 g / propylene glycol monomethyl ether acetate PGMEA) 100 g ', which can improve the brightness and contrast ratio.

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 may be represented by the general formula (2) and all others may be a halogen atom, at least one of R ⁵ to R ⁸ is represented by the general formula (2) And 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]

The colorant may further comprise a pigment.

The dye represented by Formula 1 has inherent spectroscopic characteristics in a specific wavelength region and is controlled by transparency and transmission width of a color filter manufactured using a photosensitive resin composition by a synergistic action with a pigment showing a specific hue Not only the color purity is improved, but also the color characteristics such as luminance and contrast (contrast ratio) and chemical resistance are improved.

The pigments may include red pigments, yellow pigments, blue pigments, green pigments, or combinations thereof. For example, the pigment may be a green pigment, a yellow pigment, or a combination thereof.

The red pigment may be a compound containing at least one azo group. Pigment red 254, C.I. Pigment red 242, C.I. Pigment red 214, C.I. Pigment red 221, C.I. Pigment red 166, C.I. Pigment red 220, C.I. Pigment red 248, C.I. Pigment red 262, etc. These may be used alone or in combination of two or more.

The yellow pigments have a C.I. Pigment yellow 139, C.I. Pigment yellow 138, C.I. Pigment yellow 150, etc. These may be used alone or in combination of two or more. For example, the yellow pigment is the above-mentioned C.I. Pigment Yellow 138 may be used. The C.I. Pigment Yellow 138 is good compatibility with epoxy resin.

The blue pigment may be a copper phthalocyanine blue pigment, for example, a compound classified as a pigment in a color index, such as CI Blue Index Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 And the like.

The green pigment may be a halogenated phthalocyanine green pigment, and examples thereof include CI Pigment Green 7, 36 and 58, which are classified into pigments in the color index.

The pigment may be directly added to the photosensitive resin composition according to one embodiment or may be added in the form of a pigment dispersion including a dispersant or a solvent.

At this time, as the dispersing agent that can be contained in the pigment dispersion, a nonionic dispersant, an anionic dispersant, or a cationic dispersant may be selectively used, and examples thereof include polyalkylene glycols and esters thereof; Polyoxyalkylene; Polyhydric alcohol ester alkylene oxide adducts; Alcohol alkylene oxide adducts; Etc. may be used alone or in appropriate combination. The dispersant may be included in an amount of 10 to 20 parts by weight based on 100 parts by weight of the pigment.

As the solvent that can be included in the pigment dispersion composition, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone and the like can be used. At this time, it is preferable that the content of the solvent is adjusted so that the solid content of the pigment dispersion is 5 wt% to 30 wt%.

When the colorant includes both the dye and the pigment represented by Formula 1, the dye and the pigment may be used in a weight ratio of 1: 9 to 9: 1, for example, 1: 9 to 5: 5. When they are mixed in the weight ratio range, a high contrast ratio can be obtained while maintaining color characteristics.

On the other hand, the particle diameter of the pigment can be determined in consideration of dispersion stability and pixel resolution, and for example, a pigment having an average particle diameter of 30 nm to 200 nm can be used.

The content of the colorant may be 1 wt% to 20 wt%, for example, 5 wt% to 15 wt% based on 100 wt% of the photosensitive resin composition. When the colorant is included within the above range, excellent processability and color characteristics can be obtained.

(F) Antioxidants

The photosensitive resin composition according to one embodiment may further include an antioxidant.

In the conventional dye-type photosensitive resin composition, heat resistance and chemical resistance are lower than those of a pigment-type photosensitive resin composition. To solve this problem, a metal complex in which a dye is polymerized or a metal is reacted with a dye is used. However, when the dye is polymerized, the amount of the dye used increases and the reliability of the dye may be deteriorated. When the metal complex is used, the color characteristic such as coloring power may be lowered than when the dye alone is used .

On the other hand, the photosensitive resin composition according to an embodiment further includes an antioxidant to improve the reliability and color characteristics, and at the same time, it can have excellent heat resistance and chemical resistance.

The antioxidant may be represented by the following general formula (9).

[Chemical Formula 9]

In the above formula (9)

L ¹ to L ⁸ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ¹⁷ to R ³⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,

At least one of R ¹⁷ to R ²¹ , at least one of R ²² to R ²⁶ , at least one of R ²⁷ to R ³¹ , and at least one of R ³² to R ³⁶ is a hydroxy group,

At least two of R ¹⁷ to R ²¹ , at least two of R ²² to R ²⁶ , at least two of R ²⁷ to R ³¹ , and at least two of R ³² to R ³⁶ are t-butyl groups.

The photosensitive resin composition generally generates free radicals at a post-process step such as a high temperature, thereby deteriorating the heat resistance and chemical resistance of the composition. However, the photosensitive resin composition according to one embodiment further contains the above-mentioned antioxidant to inactivate the free radicals, thereby minimizing the color change even after a severe post-processing step such as high temperature, and having excellent heat resistance and chemical resistance It is.

Specifically, the free radicals generated at high temperatures react with the surrounding oxygen (see Scheme 1), and the free radicals that react with oxygen react with the hydroxyl groups of di-t-butylphenol, a substituent contained in the antioxidant, , And is inactivated (see Scheme 2).

[Reaction Scheme 1]

R˙ + O ₂ → ROO˙

[Reaction Scheme 2]

The hydroxyl group of ROO˙ + di-t-butylphenol → ROOH

For example, each of L ¹ to L ⁸ may independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The antioxidant may be represented by the following general formula (10).

[Chemical formula 10]

For example, the antioxidant may be represented by the following general formula (11).

(11)

The content of the antioxidant may be 0.01 wt% to 1 wt%, for example, 0.01 wt% to 0.5 wt%, for example, 0.01 wt% to 0.1 wt% based on the total amount of the photosensitive resin composition (100 wt%). When the antioxidant is contained within the above range, the heat resistance and the chemical resistance are excellent while minimizing the color change.

(A) Binder resin

The photosensitive resin composition according to one embodiment includes a binder resin.

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% by weight to 30% by weight, for example, 5% by weight to 20% by weight based on the total amount of the photosensitive resin composition (100% by weight). When the binder resin is contained within the above range, the color filter is excellent in developing property and the crosslinkability is improved, so that excellent surface smoothness can be obtained.

(B) Photopolymerization  Monomer

The photosensitive resin composition according to one embodiment includes a photopolymerizable monomer such as an acrylic photopolymerizable monomer.

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

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

A commercially available product of the photopolymerizable monomer is exemplified 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 monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 1 wt% to 40 wt%, for example, 5 wt% to 25 wt% with respect to the total amount of the photosensitive resin composition (100 wt%). When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern forming step, and therefore, the photopolymerizable monomer is excellent in reliability and developability in an alkaline developer.

(C) Light curing Initiator

The photosensitive resin composition according to one embodiment includes a photopolymerization initiator.

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

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, benzoyl benzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4'-bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisobutyl Propyl thioxanthone 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) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (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 contained in an amount of 1 wt% to 15 wt%, for example, 1 wt% to 10 wt% with respect to the total amount of the photosensitive resin composition (100 wt%). When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(E) Solvent

The solvent may be a material that has compatibility with the binder resin, the photopolymerizable monomer, the photopolymerization initiator, the colorant, and the antioxidant but does not react.

The solvent is not particularly limited, but specific examples thereof 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 methyl ether, ethylene glycol ethyl ether and propylene glycol methyl 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 alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters 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, Ethyl, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of 50% by weight to 90% by weight based on the total amount of the photosensitive resin composition (100% by weight). 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.

(G) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; And at least one additive selected from a radical polymerization initiator.

The additive can be easily adjusted according to desired properties.

The coupling agent may be a silane coupling agent. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and these may be used singly or in combination of two or more Can be mixed and used.

The silane coupling agent may be used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

The photosensitive resin composition may further contain a surfactant if necessary.

Examples of the surfactant include F-482, F-484, F-478 and F-554 manufactured by DIC Corporation.

It is more preferable that the surfactant is contained in an amount of 0.01 wt% to 5 wt%, for example, 0.1 wt% to 2 wt% with respect to the total amount of the photosensitive resin composition (100 wt%). If it is out of the above range, a foreign matter may be generated after development, which is not preferable.

The photosensitive resin composition according to one embodiment is an alkali developing type which is cured by irradiation of light and can be developed into an alkaline aqueous solution. When the active ingredient is irradiated to form a pattern necessary for the color filter after the photosensitive resin composition is applied on the substrate, the reaction is caused by light. The reacted site has a lower solubility in the solvent than the unreacted site, Are selectively soluble. The solution for removing the unexposed portions is called a developer, and there are two types of such developers, organic solvent type and alkali developing type. Among them, organic solvent type causes air pollution and is harmful to human body, so it is better to use alkali developing type in environmental aspect. The photosensitive resin composition according to one embodiment can be used in an environmentally friendly manner since an alkali developing type developer can be used.

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

A method of manufacturing the color filter is as follows.

On a substrate (for example, a glass substrate) subjected to a predetermined pretreatment by a suitable method such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like to a thickness of 0.5 탆 to 10 탆, After the photosensitive resin composition described above is applied, the solvent is removed by heating on a hot plate at 90 DEG C for 150 seconds to form a photosensitive resin composition layer.

Next, light is irradiated onto the substrate on which the photosensitive resin composition layer is formed by using an exposure machine so as to form a pattern necessary for the color filter. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV of 190 to 450 nm, for example, 200 to 400 nm can be irradiated. A photoresist mask may be further used in the above irradiation step. After the pattern exposure (for example, pattern exposure with 50 mJ and 200 탆 GAP) was performed using the exposure machine, the photosensitive resin composition layer irradiated with the light source was developed (for example, developed at a developing temperature of 25 캜 for 60 seconds , Rinsing for 60 seconds, spin-drying for 25 seconds, and the developer can use a 1 wt% aqueous KOH solution). At this time, the non-exposed portion in the photosensitive resin composition layer is dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. Further, in the above step, the image pattern obtained by development is heated again (for example, the substrate on which the photosensitive resin composition layer treated with the developer is formed is heated at 230 DEG C for 20 minutes using convection oven) or cured It is possible to improve crack resistance, solvent resistance and the like.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

(Dye preparation)

Manufacturing example  1: Preparation of dye 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. 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), J = 6.8 Hz, 6H), 1.33 (m, 4H), 1.33 (m, 4H)

MS  data

HRMS (ESI-TOF) = 801

(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)

Manufacturing example  2: Preparation of the dye represented by the 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. 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), (D, J = 9.2, 5.4 Hz, 4H), 2.11 (m, 4H), 1.01

MS  data

HRMS (ESI-TOF) = 801

(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]

Manufacturing example  3: Preparation of the dye represented by the 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. 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), (D, J = 9.2, 5.4 Hz, 4H), 2.88 (m, 4H), 1.27

MS  data

HRMS (ESI-TOF) = 773

(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]

Manufacturing example  4: Preparation of the dye represented by the 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. 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), (M, 4H), 1.95-1.92 (m, 4H), 1.70-1.45 (m, 12H) ppm

MS  data

HRMS (ESI-TOF) = 825

(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]

Manufacturing example  5: Preparation of dye represented by general 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. 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

MS  data

HRMS (ESI-TOF) = 841

(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)

Manufacturing example  6: Preparation of dye represented by general 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. 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 ) ppm

MS  data

HRMS (ESI-TOF) = 869

(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]

Comparative Manufacturing Example  1: Preparation of the dye represented by the formula (12)

To a 250 mL flask was added 1.0 g of yellow dye 139, 3.0 mL of 1-bromobutane, 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 dissolved in the obtained solid in a small amount to dissolve the solid, and then hexane was added to crystallize the solid. At this time, the obtained solid was filtered and dried under vacuum to obtain a compound represented by the following general formula (12).

^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, 8H), 0.94 (t, J = 6.8 Hz, 12H) ppm

MS  data

HRMS (ESI-TOF) = 591

(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 12]

(Preparation of photosensitive resin composition)

Example  1 to Example  7 and Comparative Example  One

After dissolving the photopolymerization initiator in the solvent with the composition shown in Table 1 below, the photopolymerization initiator is thoroughly stirred at room temperature (over 30 minutes) until the photopolymerization initiator is dissolved. To this, a binder resin and a photopolymerizable monomer are added sequentially, and the mixture is stirred at room temperature for about 1 hour. To this, an antioxidant and other additives are added, and then a colorant is added, followed by stirring at room temperature for 2 hours or more. The solution was filtered three times to remove impurities to prepare photosensitive resin compositions according to Examples 1 to 7 and Comparative Example 1. The components used in the production of the photosensitive resin composition are as follows.

(A) Binder resin

Acrylic binder resin (CRG300S, SMS)

(B) Photopolymerization  Monomer

Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(C) Light curing Initiator

    Oxime compounds (IRGARCURE OXE02, BASF)

(D) Colorant

(dyes)

(D-1) The dye of Production Example 1

(D-2) The dye of Production Example 2

(D-3) The dye of Production Example 3

    (D-4) The dye of Production Example 4

    (D-5) The dye of Production Example 5

    (D-6) The dye of Production Example 6

(Pigment)

(D-7) Yellow pigment 138 (SANYO COLOR WORKS, Ltd.)

(D-8) Green pigment 58 (SKC)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) Antioxidants

    The antioxidant of formula 11 (IRGANOX 1010, BASF)

(11)

(G) Additive

Surfactant (F-554, DIC)

(Unit: wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 (A) Binder resin 10 10 10 10 10 10 10 10 (B) Photopolymerization  Monomer 10 10 10 10 10 10 10 10 (C) Light curing Initiator One One One One One One One One (D) Colorant D-1 2 4 - - - - - - D-2 - - 2 - - - - - D-3 - - - 2 - - - - D-4 - - - - 2 - - - D-5 - - - - - 2 - - D-6 - - - - - - 2 - D-7 2 - 2 2 2 2 2 4 D-8 6 6 6 6 6 6 6 6 (E) Solvent 68.45 68.45 68.45 68.45 68.45 68.45 68.45 68.45 (F) Antioxidants 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - (G) Additive 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.55 Total 100 100 100 100 100 100 100 100

(In Table 1, the binder content is based on the solid content and the colorant content is the content of only the dye and / or pigment)

Evaluation 1: Evaluation of solubility

The solubilities of the dyes represented by the above Chemical Formulas (3) to (8) and (12), yellow pigment (138) and yellow pigment (150) in 100 g of PGMEA were measured (30 ° C).

(Unit: g) coloring agent Solubility The dye represented by the general formula (3) 19.2 The dye represented by the general formula (4) 18.5 The dye represented by the general formula (5) 17.1 The dye represented by the general formula (6) 15.7 The dye represented by the general formula (7) 13.0 The dye represented by the general formula (8) 12.5 The dye represented by the general formula (12) 10.1 Yellow pigment 138 Less than 1.0 Yellow pigment 150 Less than 1.0

It can be seen from Table 2 that the dyes (Formulas 3 to 8) according to one embodiment have higher solubilities to the organic solvent than the dyes and pigments represented by Formula 12, and the photosensitive resin composition comprising the dye according to one embodiment It can be confirmed that it has excellent stability.

Evaluation 2: Coloring power  evaluation

Each of the photosensitive resin compositions of Examples 1 to 7 and Comparative Example 1 was coated on a glass substrate having a thickness of 1 mm which had been degreased and cleaned and dried on a hot plate at 90 DEG C for 3 minutes to obtain a coated film. The obtained coating film was cooled, irradiated with light at an exposure dose of 50 mJ / cm ² (based on 365 nm), and then dried in a hot air circulating drying oven at 230 ° C for 30 minutes. The thickness of the dried coating was measured (KLA-Tencor, tencor P10) and the results are shown in Table 3 below.

Film Thickness (㎛) Example 1 3.0 Example 2 3.0 Example 3 3.0 Example 4 3.0 Example 5 2.9 Example 6 2.9 Example 7 3.0 Comparative Example 1 3.3

(In Table 3, it means that the thicker the film thickness, the lower the coloring power)

Evaluation 3: Evaluation of heat resistance and chemical resistance

Each of the photosensitive resin compositions of Examples 1 to 7 and Comparative Example 1 was coated on a glass substrate having a thickness of 1 mm which had been degreased and cleaned and dried on a hot plate at 90 DEG C for 3 minutes to obtain a coated film. The obtained coating film was cooled, irradiated with light at an exposure dose of 50 mJ / cm ² (based on 365 nm), and then dried in a hot air circulating drying oven at 230 ° C for 30 minutes.

The obtained coating film was further dried for 30 minutes in a hot-air circulation type drying oven at 230 ° C, and then the luminance and color change were measured through a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). Color change △ Eab * = {(△ L *) 2 + (△ a *) 2 + (△ b *) 2} was calculated by substituting the equation ^1/2. The results are shown in Table 4 below.

The coating film obtained above was immersed in a PI solvent having a temperature raised to 80 ° C for 5 minutes, which was used in the production of a color filter, and then the luminance and color change were measured through a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 5 below.

Heat resistance Luminance Shade (Eab *) Example 1 63.5 0.89 Example 2 64.0 1.11 Example 3 63.2 0.95 Example 4 63.0 0.98 Example 5 63.3 0.92 Example 6 63.3 0.95 Example 7 63.4 0.90 Comparative Example 1 62.0 4.99

Chemical resistance Luminance Shade (Eab *) Example 1 63.0 1.33 Example 2 62.5 1.29 Example 3 62.8 1.20 Example 4 62.7 1.25 Example 5 62.8 1.30 Example 6 63.0 1.31 Example 7 62.9 1.30 Comparative Example 1 61.5 4.51

From Table 4 and Table 5, it can be confirmed that the photosensitive resin compositions of Examples 1 to 7 have better heat resistance and chemical resistance than the photosensitive resin composition of Comparative Example 1. [

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (18)

(A) a binder resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a colorant comprising a dye represented by the following formula (1);
(E) a solvent; And
(F) an antioxidant,
Wherein the antioxidant is contained in an amount of 0.01 wt% to 1 wt% based on the total weight of the photosensitive resin composition:
[Chemical Formula 1]

In Formula 1,
R ¹ to R ¹³ each independently represent 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.
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 the dye represented by Formula 1 is a yellow dye.
The method according to claim 1,
Wherein the solubility of the dye represented by Formula 1 is 10 g to 30 g per 100 g of propylene glycol monomethyl ether acetate (PGMEA) at a temperature of 25 ° C to 50 ° C.
The method according to claim 1,
Wherein the dye represented by the formula (1) is 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]

delete The method according to claim 1,
Wherein the antioxidant is a photosensitive resin composition represented by the following general formula (9)
[Chemical Formula 9]

In the above formula (9)
L ¹ to L ⁸ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,
R ¹⁷ to R ³⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,
At least one of R ¹⁷ to R ²¹ , at least one of R ²² to R ²⁶ , at least one of R ²⁷ to R ³¹ , and at least one of R ³² to R ³⁶ is a hydroxy group,
At least two of R ¹⁷ to R ²¹ , at least two of R ²² to R ²⁶ , at least two of R ²⁷ to R ³¹ , and at least two of R ³² to R ³⁶ are t-butyl groups.
9. The method of claim 8,
Each of L ¹ to L ⁸ is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
The method according to claim 1,
Wherein the antioxidant is represented by the following formula (10).
[Chemical formula 10]

The method according to claim 1,
Wherein the antioxidant is represented by the following formula (11).
(11)

delete The method according to claim 1,
Wherein the coloring agent further comprises a pigment.
14. The method of claim 13,
Wherein the pigment is a green pigment, a yellow pigment, or a combination thereof.
14. The method of claim 13,
Wherein the dye and the pigment represented by Formula 1 are contained in a weight ratio of 1: 9 to 9: 1.
The method according to claim 1,
The photosensitive resin composition may contain, based on the total weight of the photosensitive resin composition,
(A) 1 to 30% by weight of the binder resin;
(B) 1 wt% to 20 wt% of the photopolymerizable monomer;
(C) 0.1 to 10% by weight of the photopolymerization initiator;
(D) 1% to 20% by weight of the colorant;
(F) 0.01% to 1% by weight of said antioxidant; And
(E) the solvent remaining amount
.
The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; And at least one additive selected from a radical polymerization initiator.
A color filter produced by using the photosensitive resin composition of any one of claims 1 to 6, 8 to 11, and 13 to 17.