KR101426542B1 - Photosensitive resin composition, and color filter using the same - Google Patents

Abstract

(상기 화학식 1에서, R¹　내지 R¹⁰은 명세서에 정의된 바와 같다.)(A) a photosensitive resin composition comprising a dye comprising a perylene compound represented by the following formula (1), (B) a pigment, (C) an acrylic binder resin, (D) a photopolymerization initiator, (E) a photopolymerizable monomer, and A resin composition and a color filter using the resin composition are provided.
[Chemical Formula 1]

(In the above formula (1), R ¹ to R ¹⁰ are 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 colorant concentration of the photosensitive resin composition is increased in the production of a color filter in order to increase the color purity. In order to increase productivity and yield in the production process, a photosensitive resin composition having a low developing speed, Is required.

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 and the like. Recently, a pigment dispersion method is widely used.

However, the color filter manufactured by the pigment dispersion method has a limit of luminance and contrast ratio resulting from the size of the pigment particle.

On the other hand, the image sensor refers to a component of a video image pickup device that generates an image from a mobile phone camera or a digital still camera (DSC). The image sensor is classified into a charge coupled device (CCD) image sensor And complementary metal oxide semiconductor (CMOS) image sensors. The pattern size of the color filter mounted on the color image pickup device used for the solid-state image pickup device or the complementary metal oxide semiconductor is 1/100 to 1/200 times that of the color filter pattern for a liquid crystal display device. Accordingly, the increase of the resolution and the reduction of the residue are important items that determine the performance of the device.

In order to be used for an image sensor, a photosensitive resin composition composed of smaller particles is required for forming a fine pattern of a color filter.

An aspect of the present invention is to provide a photosensitive resin composition having a high luminance and a high contrast ratio.

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

(A) a dye comprising a perylene compound represented by the following formula (1); (B) a pigment; (C) an acrylic binder resin; (D) a photopolymerization initiator; (E) a photopolymerizable monomer; And (F) a solvent.

[Chemical Formula 1]

(In the formula 1,

R ¹ to R ¹⁰ are the same or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted Or a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, Or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group.

In Formula 1, R ¹ to R ⁸ are each a hydrogen atom, and R ⁹ and R ¹⁰ are the same or different from each other and each represents a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a substituted or unsubstituted C6 to C30 aryloxy . At least one of R ¹ to R ⁸ is a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to case C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a substituted or unsubstituted C6 to C30 aryloxy group, R ⁹ and R ¹⁰ are the same or another A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkyl group, a substituted or unsubstituted aryl group, Cycloalkyl groups, substituted or unsubstituted C2 to C20 heterocycloalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, or substituted or unsubstituted C6 to C30 arylox Time.

The perylene compound may be any of compounds represented by the following formulas (2-1) to (2-3).

[Formula 2-1]

(In the above formula (2-1), n ₁ to n ₆ are each an integer of 0 to 10)

[Formula 2-2]

(In the above formula (2-2)

R ¹¹ to R ¹⁴ are the same or different and each is a substituted or unsubstituted C1 to C20 alkyl group,

and n ₁₁ to n ₁₄ are each an integer of 0 to 5)

[Formula 2-3]

(In the above formula 2-3,

R ¹⁵ to R ¹⁷ are the same or different and each is a substituted or unsubstituted C1 to C20 alkyl group,

n ₁₅ to n ₁₇ are each an integer of 0 to 5)

The dye may have a maximum absorption wavelength in a wavelength region of 460 to 560 nm in spectroscopic analysis, and a transmittance in a wavelength region of 560 to 660 nm may be 80 to 100% in spectroscopic analysis.

The dye may have a thermal decomposition temperature of 250 to 500 ° C.

The dye may be contained in an amount of 0.01 to 20% by weight based on the total amount of the photosensitive resin composition, and may be specifically included in an amount of 0.05 to 10% by weight.

The dye and the pigment may be mixed in a weight ratio of 1:20 to 20: 1, specifically 1:10 to 10: 1.

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

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

The photosensitive resin composition has a high brightness and a high contrast ratio and can be applied to a color filter having excellent pattern characteristics, development processability, chemical resistance, color reproducibility and the like.

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 specified herein, "substituted" means that at least one hydrogen atom in the compound is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1- A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamoyl group, A C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 2 to C 20 alkynyl group, a C 6 to C 30 aryl group, a C 3 to C 20 cycloalkyl group, a C 3 to C 20 cycloalkenyl group, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise specified in the present specification, the term "amine derivative group" means an amine derivative group in NH ₂ present in an amine in which at least one hydrogen atom is replaced by a halogen atom, a hydroxy group, a carboxyl group, an ether group, a sulfonate group, a sulfonic acid group, Or an unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C30 aryl group.

Unless otherwise specified in the specification, the "ether group" means ROR '(wherein R and R' are the same or different and are a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group , Or a substituted or unsubstituted C6 to C30 aryl group).

"Hetero" means that at least one heteroatom of N, O, S or P is present in the ring compound, unless otherwise specified herein.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

The photosensitive resin composition according to one embodiment is a photosensitive resin composition comprising (A) a dye containing a perylene group compound, (B) a pigment, (C) an acrylic binder resin, (D) a photopolymerization initiator, (E) a photopolymerizable monomer, .

(A) Dye

The dye includes a perylene compound represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

R ¹ to R ¹⁰ are the same or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted Or a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, Or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group.

As specific examples of the above-mentioned perylene compound, R ¹ to R ¹⁰ in the general formula (1) are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted C6 to C30 aryloxy group.

More specifically, when R ¹ to R ⁸ are hydrogen atoms, R ⁹ and R ¹⁰ are the same or different from each other and are a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group , A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, Gt; C6-C30 < / RTI > aryloxy group. At least one of R ¹ to R ⁸ is a substituent selected from the group consisting of a halogen atom, a cyano group, a hydroxyl group, an ether group, an amine group or an amine derivative group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, or unsubstituted C3 to C20 cycloalkyl group, a substituted or case unsubstituted C2 to C20 heterocycloalkyl group, or a substituted or unsubstituted C6 to C30 aryloxy group, R ⁹ and and R ¹⁰ is the same as or different from each other, a halogen atom , A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, An unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryloxy group, .

The most specific example of the above-mentioned perylene compound is any one of the compounds represented by the following formulas (2-1) to (2-3).

[Formula 2-1]

(In the above formula (2-1), n ₁ to n ₆ are each an integer of 0 to 10)

[Formula 2-2]

(In the above formula (2-2)

R ¹¹ to R ¹⁴ are the same or different and each is a substituted or unsubstituted C1 to C20 alkyl group,

and n ₁₁ to n ₁₄ are each an integer of 0 to 5)

[Formula 2-3]

(In the above formula 2-3,

R ¹⁵ to R ¹⁷ are the same or different and each is a substituted or unsubstituted C1 to C20 alkyl group,

n ₁₅ to n ₁₇ are each an integer of 0 to 5)

The dye may be a red dye.

The dye is excellent in solubility in an organic solvent, and unlike a pigment having a particle property, the dye has no particle property in a solution state or has a very small primary particle diameter of several nanometers or less and can have high durability. By introducing such dyes, it is possible to compensate the lowering of the contrast ratio and luminance, which are problems of the pigment dispersion method which is mainly used in the production of color filters.

The dye may have a maximum absorption wavelength in a wavelength region of 460 to 560 nm in spectroscopic analysis, and a transmittance in a wavelength region of 560 to 660 nm may be 80 to 100% in spectroscopic analysis. High brightness can be exhibited when having the above range of characteristics.

The dye has high heat resistance, and the thermal decomposition temperature may be 250 ° C or higher, specifically 250 ° C to 500 ° C.

The dyes having the above characteristics can be usefully used for color filters such as LCDs and LEDs that exhibit high brightness and high contrast ratio in a desired color coordinate.

The dye may further include azo dyes and xanthene dyes for dyeing.

The dye may be contained in an amount of 0.01 to 20% by weight based on the total amount of the photosensitive resin composition, and may be specifically included in an amount of 0.05 to 10% by weight. If the dye is included in the above range, it can have a high luminance and contrast ratio.

(B) Pigment

As the pigment, both an organic pigment and an inorganic pigment can be used. Specific examples include red Dipyrrolopyrrole pigments such as C. I. Red Pigments 254, 255, 264, 270, 272; C. I. pigments such as Red Pigment 177, 89; C. I. yellow isoindoline pigments such as yellow pigments 139; C. yellow quinophthalone-based pigments such as yellow pigments 138; Yellow nickel complex pigments such as C.I. yellow pigment 150, and the like, and they may be used alone or in combination of two or more.

The pigment can be used by reducing the primary particle diameter. This is specifically exemplified by a method in which a water-soluble inorganic salt and a wetting agent are mixed and finely kneaded in a kneader at a high pressure to reduce the primary particle diameter to less than 70 nm; a method in which the water-soluble inorganic salt and wetting agent are dissolved in an acid such as sulfuric acid, A method of reducing the primary particle diameter of the pigment using an acid pasting method or a method of reducing the primary particle diameter of the pigment by dry milling the pigment for a long time using a high-speed sand mill or the like may be used, but the present invention is not limited thereto . It is also possible to use commercially available pigments which have already reduced the primary particle diameter.

The primary particle diameter (D50) of the pigment may be 30 to 70 nm. When a pigment having the primary particle diameter in the above range is used, heat resistance, chemical resistance, durability, etc. are improved after forming a pixel.

The pigment may be contained in the photosensitive resin composition in the form of a dispersion. The pigment dispersion may be composed of the pigment, the solvent, the dispersing agent, the binder resin, and the like.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used. Among them, propylene glycol methyl ether acetate is preferably used .

The dispersant helps to uniformly disperse the pigment in the dispersion, and any nonionic, anionic or cationic dispersant may be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts Water, alkylamine, and the like. These may be used alone or in combination of two or more.

The binder resin may use an acrylic resin including a carboxyl group, which not only improves the stability of the pigment dispersion but also improves the patterning of pixels.

The primary particle diameter of the pigment may be 10 to 70 nm. When the primary particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent and the resolution of the pixel is also excellent.

The secondary particle diameter of the pigment is not particularly limited, but may be 200 nm or less, in particular 70 to 100 nm, considering the resolution of the pixel.

The pigment may be contained in an amount of 0.1 to 30% by weight based on the total amount of the photosensitive resin composition, specifically, 1 to 20% by weight. When the pigment is included in the above range, coloring property and developability are excellent.

When the dye and the pigment are mixed, they can be mixed in a weight ratio of 1:20 to 20: 1, specifically 1:10 to 10: 1. When mixed in the above-mentioned ratio range, they can have a high luminance and a high contrast ratio, and can exhibit desired color characteristics.

(C) Acrylic binder resin

The acrylic binder resin may contain a first ethylenic unsaturated monomer 　 And a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

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 to 50% by weight based on the total amount of the acrylic binder resin, specifically 10 to 40% by weight.

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 methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used alone or in combination of two or more.

The weight average molecular weight of the acrylic binder resin may be 3,000 to 150,000, specifically 5,000 to 50,000, and more specifically 20,000 to 30,000. When the weight average molecular weight of the acrylic binder resin is in the range described above, it has good adhesion with the substrate, good physical and chemical properties, and good viscosity.

The acid value of the acrylic binder resin may be 15 to 60 mgKOH / g, and specifically 20 to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, excellent pixel resolution can be obtained.

The acrylic binder resin may be contained in an amount of 0.05 to 40% by weight based on the total amount of the photosensitive resin composition, specifically 0.1 to 20% by weight. When the binder resin is contained in the pigment dispersion for stable dispersion of the pigment, the content of the acrylic binder resin is further reduced. When the acrylic binder resin is contained within the above range, the color filter is excellent in developability in the production of a color filter, and the cross-linkability is improved, whereby an excellent surface smoothness can be obtained.

(D) a photopolymerization initiator

The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition. Examples of the photopolymerization initiator include an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, a oxime compound, Can be used.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one can be used.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, 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- Orcanthon and the like can be used.

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 type compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s- triazine, 2- (3 ', 4'-dimethoxy (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis (trichloromethyl) 6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like can be used.

Examples of the oxime compounds include O-acyloxime compounds such as 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Can 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 1- (4-phenylsulfanylphenyl) Acetate and the like can be used.

In addition to the photopolymerization initiators of the above types, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, and imidazole compounds can also be used as photopolymerization initiators.

The photopolymerization initiator is preferably 0.1 to 20% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently during exposure in the pattern formation process for producing a color filter, which results in excellent sensitivity, good pattern straightness, excellent solubility in solvent and storage stability, The reaction initiator does not remain and the decrease in the transmittance can be prevented.

(E) Photopolymerizable monomer

As the photopolymerizable monomer, a polyfunctional monomer having two or more hydroxyl groups may be used. Specific examples of the photopolymerizable monomer include glycerol acrylate, dipentaerythritol hexaacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol acrylate, pentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, But are not limited to, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate , 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Acrylate and the like.

The photopolymerizable monomer may be used in an amount of 0.5 to 20% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the pattern characteristic is excellent such as the edge of the pattern is formed cleanly when the color filter is manufactured, and the developability to the alkaline developer is excellent.

(F) Solvent

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 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-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, 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 ethyl 2-hydroxypropionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included as the balance relative to the total amount of the photosensitive resin composition, specifically, 20 to 90% by weight. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coatability and excellent flatness can be maintained in a film having a thickness of 2 mu m or more.

(G) Other additives

The photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots, spots, leveling, 3-amino-1,2-propanediol; A silane-based coupling agent having a vinyl group or (meth) acryloxy group; And the like. The amount of these additives to be used can be easily controlled depending on the desired physical properties.

The photosensitive resin composition may further include a surfactant as an additive to uniformly disperse the pigment in the solvent and improve leveling performance.

The surfactant may be a fluorine-based surfactant.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 to 10,000, and more specifically, a weight average molecular weight of 6,000 to 10,000. The fluorine-based surfactant may have a surface tension of 18 to 23 mN / m (measured in 0.1% polyethylene glycol methyl ether acrylate (PEGMEA) solution). When the weight average molecular weight and the surface tension of the fluorine-based surfactant are within the above range, the leveling performance can be improved, the stain property at the time of high speed coating is excellent, Thereby imparting excellent properties to the slit coating.

Specific examples of the fluorine-based surfactant include F-482, F-484 and F-478 of DIC Company, but are not limited thereto.

The surfactant may be a silicone surfactant together with the fluorochemical surfactant.

Specific examples of the silicone surfactant include TSF400, TSF401, TSF410, and TSF4440 of Toshiba Silicones, but are not limited thereto.

In addition, the photosensitive resin composition may further contain an epoxy compound as an additive for improving adhesion and the like.

Examples of the epoxy compound include epoxy novolac acrylate carboxylate resin, orthocresol novolak epoxy resin, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, or a combination thereof .

When the epoxy compound is further included, it may further include a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator.

The epoxy compound may be used in an amount of 0.01 to 5 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 adhesion and other properties can be improved in terms of storage stability and economy.

The method of producing the photosensitive resin composition is not particularly limited, but specifically a photosensitive resin composition can be prepared by mixing the above-mentioned dyes, pigments, acrylic binder resin, photopolymerization initiator, photopolymerizable monomer, solvent and optionally additives .

According to another embodiment, there is provided a color filter made from the photosensitive resin composition.

Such a color filter can be manufactured according to a conventional method. Specifically, the above-mentioned photosensitive resin composition is applied on a glass substrate to a thickness of 2 to 4 탆 by a suitable method such as spin coating, roller coating, slit coating . After the application, UV light, electron beam or X-ray is irradiated to form a pattern necessary for the color filter. The UV light has a wavelength range of 190 to 450 nm, specifically 200 to 400 nm. Then, when the coating layer is treated with an alkali developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the image color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. Further, in the above process, the image pattern obtained by development may be further heated or cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

The contrast ratio of the photosensitive resin composition measured using the obtained color filter pattern may be 9000 or more. The contrast ratio is a value calculated according to the following Equation 1 after measuring the amount of light when the polarizing plate is opened and closed by using Contrast tester CT-1 manufactured by Tsubosaka.

[Equation 1]

Contrast ratio = L _open / L _close

L _open : the amount of light when the polarizing plate is opened

L _close : the amount of light when the polarizing plate is closed

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.

(Preparation of photosensitive resin composition)

The specifications of the components used in the production of the photosensitive resin composition are as follows.

(A) Dye

(A-1) Synthesis Example 1

0.98 g (0.0025 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride and 0.766 g (0.00575 mol, 2.3 equivalents) 60 ml of m-cresol and 10 ml of isoquinoline were slowly added to the reaction mixture under a nitrogen gas atmosphere. The reaction is then refluxed at 100 ° C. for 4 hours, 120 ° C. for 6 hours, 150 ° C. for 5 hours, and 200 ° C. for 2 hours and then cooled to room temperature. Then, 100 ml of methanol is added to the reaction mixture (dissolved in methanol), and then methanol and m-cresol are all evaporated using a rotary distillation apparatus, followed by drying in an oven for one day. The dried product was dissolved in methylene chloride (CH ₂ Cl ₂ ), washed repeatedly with water and 5% aqueous sodium hydroxide solution, and then passed through magnesium sulfate (MgSO ₄ ) to remove methylene chloride using a rotary distillation apparatus do. After drying in an oven for one day, methanol is added to precipitate, and the mixture is stirred for 2 hours. The resulting precipitate is filtered under reduced pressure, and then dried in an oven for one day to obtain a red dye represented by the following formula (3-1).

[Formula 3-1]

(A-2) Synthesis Example 2

A red dye represented by the following Chemical Formula 3-2 was prepared in the same manner as in Synthesis Example 1, except that aminoacetal was not used in Synthesis Example 1.

[Formula 3-2]

(A-3) Synthesis Example 3

(0.0081 mol) of N, N'-bis (2,6-diisopropylphenyl) -1,7-dibromopherylene-3,4,9,10-tetracarboxydiimide and 2,4,6 -trimethylphenyl boronic acid of 10.6g (0.0646mol) into a mixture of ethanol (8.2ml), benzene (47ml) and distilled water _{(23ml), Pd (PPh 3} ) 4 466mg and Na ₂ CO ₃ 2.56g (0.0242mol) Lt; / RTI > The temperature is then raised to 80 DEG C under nitrogen gas and refluxed for 120 hours. When the reaction is completed, the resultant is slowly poured into 400 ml of distilled water and extracted with 300 ml of methylene chloride. The extract is passed through magnesium sulfate to completely remove water, the methylene chloride is evaporated with a rotary distillation apparatus, and the obtained product is dried in a vacuum oven for one day. The dried product is subjected to column purification using methylene chloride to obtain a red dye represented by the following Chemical Formula 3-3.

[Formula 3-3]

(A-4) Synthesis Example 4

3.0 g (0.0038 mol) of N, N'-bis (2,6-diisopropylphenyl) -1-bromopheylene-3,4,9,10-tetracarboxydiimide and 1.14 g (0.0076 mol) are added to 40 ml of N-methylpyrrolidone (NMP) and 2.1 g (0.0152 mol) of K2CO3 are added. The temperature is then raised to 120 DEG C under a nitrogen gas and refluxed for 6 hours. When the reaction is complete, cool to room temperature and pour slowly into 400 ml of 10% aqueous hydrochloric acid solution. The resulting precipitate is filtered under reduced pressure, washed several times with distilled water until pH is 7, and dried in a vacuum oven for one day. The dried product is subjected to column purification using methylene chloride to obtain a red dye represented by the following Chemical Formula 3-4.

[Chemical Formula 3-4]

(B) Pigment

(B-1) C.I. Pigment Yellow 150 was used.

(B-2) C.I. Pigment Red 177 was used.

(B-3) C.I. Pigment Red 254 was used.

(C) Acrylic binder resin

A methacrylic acid / benzyl methacrylate copolymer having a weight average molecular weight of 22,000 (mixing weight ratio 15/85) was used.

(D) a photopolymerization initiator

1,2-octanedione and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one were used. 　

(E) Photopolymerizable monomer

Dipentaerythritol hexaacrylate was used.

(F) Solvent

Propylene glycol monomethyl ether acetate and cyclohexanone were used.

Example 1

1% by weight of 1,2-octanedione as the photopolymerization initiator (D) and 2% by weight of 2-dimethylamino-2- (4-methylpentanoic acid) as the solvent (F) were added to 35% by weight of propylene glycol monomethyl ether acetate and 40% -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one dissolved therein and stirred at room temperature for 2 hours. 4 wt% of the red dye (A-1) represented by Formula 3-1, 11.5 wt% of the pigment (B-1), 2 wt% of the acrylic binder resin (C) ) Was added thereto and stirred at room temperature for 2 hours. The solution was filtered three times and impurities were removed to prepare a photosensitive resin composition.

Example 2

The procedure of Example 1 was repeated except that the red dye (A-2) represented by Formula 3-2 was used instead of the red dye (A-1) represented by Formula 3-1 To prepare a photosensitive resin composition.

Example 3

The procedure of Example 1 was repeated except that the red dye (A-3) represented by Formula 3-3 was used instead of the red dye (A-1) represented by Formula 3-1 To prepare a photosensitive resin composition.

Example 4

The procedure of Example 1 was repeated except that the red dye (A-4) represented by Formula 3-4 was used instead of the red dye (A-1) represented by Formula 3-1 To prepare a photosensitive resin composition.

Comparative Example 1

1% by weight of 1,2-octanedione as the photopolymerization initiator (D) and 2% by weight of 2-dimethylamino-2- (4-methylpentanoic acid) as the solvent (F) were added to 45% by weight of propylene glycol monomethyl ether acetate and 40% -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one dissolved therein and stirred at room temperature for 2 hours. 2% by weight of the red dye (A-1) represented by Formula 3-1, 3.5% by weight of the acrylic binder resin (C) and 8% by weight of the photopolymerizable monomer (E) . The solution was filtered three times and impurities were removed to prepare a photosensitive resin composition.

Comparative Example 2

Except that the red dye (A-2) represented by Formula 3-2 was used instead of the red dye (A-1) represented by Formula 3-1 in Comparative Example 1, To prepare a photosensitive resin composition.

Comparative Example 3

The procedure of Comparative Example 1 was repeated except that the red dye (A-3) represented by Formula 3-3 was used instead of the red dye (A-1) represented by Formula 3-1 To prepare a photosensitive resin composition.

Comparative Example 4

Except that the red dye (A-4) represented by Formula 3-4 was used instead of the red dye (A-1) represented by Formula 3-1 in Comparative Example 1, To prepare a photosensitive resin composition.

Comparative Example 5

1% by weight of 1,2-octanedione as the photopolymerization initiator (D) and 2% by weight of 2-dimethylamino-2- (4-methylpentanoic acid) as the solvent (F) were added to 16% by weight of propylene glycol monomethyl ether acetate and 40% -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one dissolved therein and stirred at room temperature for 2 hours. 35% by weight of the red pigment (B-2), 2.5% by weight of the acrylic binder resin (C) and 5% by weight of the photopolymerizable monomer (E) were added thereto and stirred at room temperature for 2 hours. The solution was filtered three times and impurities were removed to prepare a photosensitive resin composition.

Comparative Example 6

A photosensitive resin composition was prepared in the same manner as in Comparative Example 5 except that the red pigment (B-3) was used instead of the red pigment (B-2) in Comparative Example 5.

(Pattern formation for color filter)

The photosensitive resin composition prepared in Examples 1 to 4 and Comparative Examples 1 to 5 was coated on a glass substrate having a thickness of 2 m and degreased and cleaned and dried on a hot plate at 90 DEG C for 2 minutes to form a film . Subsequently, the coated film was exposed to light using a high-pressure mercury lamp having a wavelength of 365 nm, and then dried for 20 minutes by hot-air circulation drying at 160 DEG C to obtain a color filter pattern.

Experimental Example 1: Evaluation of spectral characteristics of photosensitive resin composition

The color coordinates, the luminance and the contrast ratio were measured by the following method using the color filter pattern obtained above, and the results are shown in Table 1 below.

(1) Measurement of color coordinates (x and y) and luminance (Y): Measured using a spectrophotometer (Otsuka electronic, MCPD3000).

(2) Measurement of contrast ratio:

Contrast ratio tester CT-1 of Tsubosaka, a contrast ratio measuring instrument, was used to measure the amount of light when the polarizer was opened and closed, and then the contrast ratio was calculated according to the following equation (1). The results of the contrast ratio measurement are shown in Table 3 below.

[Equation 1]

Contrast ratio = L _open / L _close

L _open : the amount of light when the polarizing plate is opened

L _close : the amount of light when the polarizing plate is closed

Color coordinates Luminance Contrast ratio x y Y Example 1 0.655 0.336 19.8 11000 Example 2 0.655 0.335 19.7 11000 Example 3 0.655 0.327 17.4 13000 Example 4 0.655 0.334 20.0 12000 Comparative Example 1 0.526 0.282 21.6 6400 Comparative Example 2 0.447 0.221 22.2 4500 Comparative Example 3 0.504 0.236 18.3 7100 Comparative Example 4 0.557 0.281 21.5 8300 Comparative Example 5 0.655 0.302 14.6 10600 Comparative Example 6 0.655 0.334 16.9 5600

From Table 1 above, it can be seen that, in Examples 1 to 4 including a dye, a pigment, an acrylic binder resin, a photopolymerization initiator, a photopolymerizable monomer and a solvent containing a perylene compound in accordance with an embodiment, Compared with the case of Comparative Examples 5 and 6, it can be seen that the luminance and the contrast ratio are both high. Further, in the case of Comparative Examples 1 to 4 in which the pigment is not used, the luminance is somewhat higher than that in Examples 1 to 4, but the contrast ratio is remarkably decreased.

The result of the high contrast ratio can be explained by the high transmittance of the dye, and the result of the high contrast ratio indicates that the dye has solubility in an organic solvent, unlike the dispersed particles of the pigment, And that the primary particle size is very small as compared to the pigment, thereby reducing unnecessary light scattering.

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 (10)

(A) a dye comprising a perylene compound represented by the following formula (2-1);
(B) a pigment;
(C) an acrylic binder resin;
(D) a photopolymerization initiator;
(E) a photopolymerizable monomer; And
(F) a solvent.
[Formula 2-1]

(In the above formula (2-1), n ₁ to n ₆ are each an integer of 0 to 10)
delete delete delete The method according to claim 1,
Wherein the dye has a maximum absorption wavelength in a wavelength region of 460 to 560 nm upon spectroscopic analysis.
The method according to claim 1,
Wherein the dye has a transmittance in a wavelength range of 560 to 660 nm in a spectral analysis of 80% to 100%.
The method according to claim 1,
Wherein the dye has a thermal decomposition temperature of 250 to 500 ° C.
The method according to claim 1,
Wherein the dye is contained in an amount of 0.01 to 20% by weight based on the total amount of the photosensitive resin composition.
The method according to claim 1,
Wherein the dye and the pigment are mixed in a weight ratio of 1:20 to 20: 1.
A color filter produced by using the photosensitive resin composition of any one of claims 1 to 9.