KR20100105190A - Color photo-sensitive resin composition and color filter - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition is provided to obtain an excellent color reproduction property, brightness, and a contrast ratio and to be used for manufacturing a color filter having superior heat resistance and high resolution. CONSTITUTION: A colored photosensitive resin composition comprises 1-40 weight% of a coloring agent, 0.5-30 weight% of an alkali soluble resin, 0.5-30 weight% of a photopolymerizable monomer, 0.1-10 weight% of a photopolymerizable initiator, and a solvent. The coloring agent includes 5-100.0 parts by weight of one coloring material which is selected from a chemical formula 1, chemical formula 2, chemical formula 3, or chemical formula 4 based on 100.0 parts by weight of a pigment.

Description

Colored photosensitive resin composition and color filter {Color Photo-sensitive Resin Composition And Color Filter}

The present invention relates to a colored photosensitive resin composition and a color filter, and more particularly, to a colored photosensitive resin composition capable of producing a high resolution color filter having excellent color reproducibility, brightness and contrast ratio, high transmittance, and good heat resistance and light resistance. It is about.

Recently, as the spread of large screen liquid crystal display devices has increased, consumers are demanding a new performance improvement for better liquid crystal display devices than ever before. In the liquid crystal display device, color filters are the most important component for implementing color and are a process for productivity. Research to increase margins is ongoing. In addition, in the case of the large-screen liquid crystal display, the colorant concentration of the color photosensitive resin composition is increased during the production of the color filter in order to increase the color purity. A resin composition is required.

As a method for producing a color filter using a colored photosensitive resin composition, a pattern is formed, and then, the pattern is dyed with a dye, a voltage is applied to the formed pattern, and an electrodeposition method for ionizing the colored photosensitive resin composition to produce the pattern is carried out. The pigment dispersion method which forms a pattern using the coloring photosensitive resin composition in which the pigment was atomized with the printing method which forms the form, and a coloring agent is used. Among them, the color filter produced by the pigment dispersion method is widely used because it is the most economical, convenient, and reliable. However, in order to manufacture a color filter having excellent color purity, a colored photosensitive resin composition having a high pigment concentration may be used as a colorant. In this case, the dispersion stability of the colored photosensitive resin composition may be lowered, and a margin of development and sensitivity in the manufacturing process is lowered.

In order to solve this problem, conventionally, a colorant is prepared by using a green dye of a metal halide phthalocyanine sulfonic acid such as octachloronickel phthalocyanine sulfonic acid and a cobalt phthalocyanine sulfonic acid and a yellow organic dye, or by mixing a phenylated phthalocyanine and a yellow organic dye. Although a method of manufacturing a filter has been attempted, there is a problem in that reliability such as heat resistance and light resistance is inferior.

In addition, the Republic of Korea Patent Publication No. 2007-042719 introduces a technique for manufacturing a color filter by mixing a pigment dispersion in which the pigment is atomized and a solvent-type dye soluble in a solvent, but commercially available solvent-type dyes are inferior in color purity, It has a disadvantage that the color characteristics are not excellent after manufacturing because it has a spectral characteristic that is not suitable for the color filter.

One embodiment of the present invention is to provide a color photosensitive resin composition which is excellent in color reproducibility, brightness and contrast ratio, high transmittance, high heat resistance and light resistance when producing a pattern of a color filter.

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

The technical problems to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical problems not mentioned will be clearly understood by the average technician from the following description.

According to one embodiment of the present invention, a coloring agent; Alkali-soluble resins; Photopolymerizable monomers; Photopolymerization initiator; And a solvent, wherein the coloring agent provides a colored photosensitive resin composition comprising a pigment and at least one coloring material selected from the group consisting of compounds of the following formula (1).

[Formula 1]

(In the formula 1,

And, ^- X ₁ and X ₂ are the same as or different from each other, and, independently, SO ₃ ^- or COO

Y ₁ and Y ₂ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula A,

B is a halogen element,

n ₁ and n ₂ are each independently an integer of 1 to 4,

m ₁ and m ₂ are each independently an integer of 1 to 4,

k ₁ and k ₂ are each independently an integer of 0 to 3,

m ₁ + k ₁ = m ₂ + k ₂ = 4)

[Formula 2]

(3)

(In Chemical Formulas 2 and 3,

And, ^- X ₃ to X ₆ and is the same as or different from each other, each independently, SO ₃ ^- or COO

Y ₃ to Y ₆ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula (A),

n ₃ to n ₆ are each independently an integer of 1 to 4,

m ₃ to m ₆ are each independently 0 to 1,

m ₃ + m ₄ ≥ 1 and m ₅ + m ₆ ≥ 1)

[Formula 4]

(In Formula 4,

And, ^- X ₇ to X ₁₀ are the same as or different from each other, and, independently, SO ₃ ^- or COO

Y ₇ to Y ₁₀ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula (A),

B is a halogen element,

n ₇ to n ₁₀ are each independently an integer of 1 to 4,

m ₇ , m _8, m ₉ , m ₁₀ are each independently 0 to 1,

m ₇ + m ₈ + m ₉ + m ₁₀ ≥ 1,

k ₇ to k ₁₀ are each independently an integer of 0 to 3,

m ₇ + k ₇ = m ₈ + k ₈ = m ₉ + k ₉ = m ₁₀ + k ₁₀ = 4)

[Formula A]

(In Formula A,

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted group Substituted alkynyl groups having 2 to 30 carbon atoms, substituted or unsubstituted oxyalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or Unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkenyl groups having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms 2 to 30 30 heteroalkynyl group, substituted or unsubstituted heterooxyalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted carbon It is selected from the group consisting of a heteroaryl group having 1 to 30, a substituted or unsubstituted heteroaralkyl group having 2 to 30 carbon atoms and derivatives or polymers thereof.)

According to another embodiment of the present invention, there is provided a color filter manufactured using the colored photosensitive resin composition.

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

As the colored photosensitive resin composition of the present invention, a high-resolution color filter having excellent color reproducibility, brightness and contrast ratio, high transmittance, and good heat resistance and light resistance can be produced.

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 defined herein, "alkyl group" means an alkyl group having 1 to 30 carbon atoms, "alkenyl group" means an alkenyl group having 2 to 30 carbon atoms, and "alkynyl group" means 2 to 30 carbon atoms. An alkynyl group means an "oxyalkyl group", which means an oxyalkyl group having 1 to 30 carbon atoms, "cycloalkyl group" means a cycloalkyl group having 3 to 30 carbon atoms, and an "aryl group" means an aryl group having 6 to 30 carbon atoms. "Alkyl group" means an aralkyl group having 7 to 30 carbon atoms, "heteroalkyl group" means a heteroalkyl group having 1 to 30 carbon atoms, "heteroalkenyl group" means a heteroalkenyl group having 2 to 30 carbon atoms "Heteroalkynyl group" means a heteroalkynyl group having 2 to 30 carbon atoms, "heterooxyalkyl group" means a heterooxyalkyl group having 1 to 30 carbon atoms, and a "heterocycloalkyl group" means 3 to 30 carbon atoms. It means a heterocycloalkyl group, "heteroaryl group" means a heteroaryl group of 6 to 30 carbon atoms, "heteroaralkyl group" means a heteroaralkyl group of 7 to 30 carbon atoms.

In the present specification, "substituted" means, unless otherwise defined, at least one hydrogen atom of the functional group of the present invention is a halogen atom (F, Cl, Br, or I), hydroxy group, nitro group, cyano group, imino group ( = NH, = NR, and R are alkyl groups having 1 to 10 carbon atoms, amino groups (-NH ₂ , -NH (R '), -N (R ") (R"'), and R 'to R "', respectively) Independently an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine or hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A substituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms and a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms Substituted with one or more substituents selected from the group consisting of it means.

In addition, hetero herein means, unless otherwise defined, that the carbon atom is substituted with any one atom selected from the group consisting of N, O, S, Si and P.

According to one embodiment of the present invention, the coloring photosensitive resin composition of the present invention is a coloring agent (A); Alkali-soluble resin (B); Photopolymerizable monomer (C); Photopolymerization initiator (D); And a solvent (E).

Hereinafter, the present invention will be described in more detail.

(A) colorant

First, in the coloring photosensitive resin composition according to the present invention, one or more coloring materials (A-1) and pigments (A-2) selected from the group consisting of compounds of the following Chemical Formulas 1 to 4 may be used as colorants.

(A-1) coloring substance

In the present invention, a coloring material that can be dissolved in one or more solvents selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4 is used as the colorant.

[Formula 1]

(In the formula 1,

And, ^- X ₁ and X ₂ are the same as or different from each other, and, independently, SO ₃ ^- or COO

Y ₁ and Y ₂ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals selected from the group consisting of Li ⁺ , Na ⁺ and K ⁺ ; And it is selected from the group consisting of ammonium ions represented by the formula (A),

B is a halogen element,

n ₁ and n ₂ are each independently an integer of 1 to 4,

m ₁ and m ₂ are each independently an integer of 1 to 4,

k ₁ and k ₂ are each independently an integer of 0 to 3,

m ₁ + k ₁ = m ₂ + k ₂ = 4)

[Formula 2]

(3)

(In Chemical Formulas 2 and 3,

And, ^- X ₃ to X ₆ and is the same as or different from each other, each independently, SO ₃ ^- or COO

Y ₃ to Y ₆ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals selected from the group consisting of Li ⁺ , Na ⁺ and K ⁺ ; And it is selected from the group consisting of ammonium ions represented by the formula (A),

n ₃ to n ₆ are each independently an integer of 1 to 4,

m ₃ to m ₆ are each independently 0 to 1,

m ₃ + m ₄ ≥ 1 and m ₅ + m ₆ ≥ 1)

[Formula 4]

(In Formula 4,

And, ^- X ₇ to X ₁₀ are the same as or different from each other, and, independently, SO ₃ ^- or COO

Y ₇ to Y ₁₀ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula (A),

B is a halogen element,

n ₇ to n ₁₀ are each independently an integer of 1 to 4,

m ₇ to m ₁₀ are each independently 0 to 1,

m ₇ + m ₈ + m ₉ + m ₁₀ ≥ 1,

k ₇ to m ₁₀ are each independently an integer of 0 to 3,

m ₇ + k ₇ = m ₈ + k ₈ = m ₉ + k ₉ = m ₁₀ + k ₁₀ = 4)

[Formula A]

(In Formula A,

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted group Substituted alkynyl groups having 2 to 30 carbon atoms, substituted or unsubstituted oxyalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or Unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkenyl groups having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms 2 to 30 30 heteroalkynyl group, substituted or unsubstituted heterooxyalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted carbon It is selected from the group consisting of a heteroaryl group having 1 to 30, a substituted or unsubstituted heteroaralkyl group having 2 to 30 carbon atoms and derivatives or polymers thereof.)

More specifically, examples of the R ₁ to R ₄ include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl (pentyl), hexyl, ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl , Dodecyl, hexadecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, methoxyethyl, cyanoethyl, ethoxy, butoxy, hexyloxy, methoxyethoxyethyl , Methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, pyrrole, imidazole, pyridine, carboxymethyl, trimethoxy Silylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and derivatives thereof, and polymer compounds such as polyallylamine or polyethyleneimine can be used.

Preferably, at least one coloring material selected from the group consisting of Chemical Formulas 1 to 4 according to the present invention is included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the pigment, and when the content is less than 5 parts by weight, the luminance may be reduced. If it exceeds 50 parts by weight, the solvent may decrease in the solvent and the contrast ratio may fall.

(A-2) Pigment

In the present invention, a pigment is used as a colorant together with a coloring material which is soluble in at least one solvent selected from the group consisting of the compounds of Formulas 1 to 4.

The pigment of the present invention is an organic pigment, and may be appropriately selected and used according to the application purpose of the color filter. Examples are compounds classified as Pigments according to The Society of Dyers and Colorists (C.I.), specifically, C.I. Pigment Yellow 83, C.I. Pigment Yellow 128, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 175 and C.I. Yellow pigment of Pigment Yellow 185; C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36 and C.I. Purple pigment of Pigment Violet 38; C.I. Pigment Red 177, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264 and C.I. Red pigment of Pigment Red 265; C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6 and C.I. Blue pigment of Pigment Blue 60; C.I. Pigment Green 7 and C.I. Green pigment of Pigment Green 36; and C.I. Pigment Black 1 and C.I. Black pigment compounds of Pigment Black 7 may be used, and may be used alone or in combination of two or more.

In the present invention, if necessary, the primary particle size is less than 70 nm by mixing the water-soluble inorganic salt and the humectant as a means for making the primary particle diameter of the pigment small and miniaturizing through kneading in a high pressure kneader. Alternatively, the size of the primary particles of the pigment may be reduced by using an acid-pasting method in which small particles are obtained by dissolving in an acid such as sulfuric acid and re-precipitating again in a poor solvent. In addition, a method of reducing the size of the primary particles of the pigment by dry grinding the pigment for a long time with a high-speed sand mill, etc. may be used. It is possible to use commercially available pigments by reducing the size of the primary particles, but it is preferable to use a pigment having an average particle size (D50) of 30 to 70 nm, and if the particle size is less than 30 nm, the pixel After formation, problems such as heat resistance, chemical resistance, adhesion strength, etc. may occur, and if it exceeds 70 nm, the brightness may decrease.

It is preferable that the usage-amount of the said pigment is 0.5 to 25 weight% with respect to the coloring photosensitive resin composition of this invention. When the content of the pigment is less than 0.5% by weight, the coloring effect is insignificant and the color reproducibility is lowered. When the content of the pigment is more than 25% by weight, the developing performance is lowered, and the brightness may be lowered.

In addition, the colorant is preferably contained in an amount of 1 to 40% by weight based on the total amount of the coloring photosensitive resin composition of the present invention, and excellent color reproducibility, brightness and contrast ratio in the above range, high transmittance, high heat resistance and high light resistance. A color filter can be manufactured.

(B) alkali soluble resin

In the present invention, the alkali-soluble resin is the first ethylenically unsaturated monomer And copolymers of second ethylenically unsaturated monomers copolymerizable therewith.

As the first ethylenically unsaturated monomer, an ethylenically unsaturated monomer containing one or more carboxyl groups may be used. Specifically, in the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof Can be selected and used.

The weight ratio of the first ethylenically unsaturated monomer is preferably in the range of 10 to 40%, preferably 20 to 30% of the total copolymer.

Examples of the second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer include an alkenyl aromatic monomer, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid amino alkyl ester compound, a carboxylic acid vinyl ester compound, and an unsaturated carboxylic acid. It can select from the group which consists of a glycidyl ester compound, a vinyl cyanide compound, an unsaturated amide compound, and a combination thereof.

Representative examples of the alkenyl aromatic monomers include styrene, α-methyl styrene, vinyl toluene, vinyl benzyl methyl ether, and the like. Examples of unsaturated carboxylic acid ester compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, benzyl acryl Latex, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, and the like. Representative examples of unsaturated carboxylic acid amino alkyl ester compounds include 2-amino ethyl acrylate, 2 -Amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate , 2-dimethyl amino ethyl methacrylate, and the like, and typical examples of the carboxylic acid vinyl ester compounds include vinyl acetate and vinyl benzoate, and typical examples of the unsaturated carboxylic acid glycidyl ester compounds are glycy. Diyl acrylate, glycidyl methacrylate, and the like. Representative examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Representative examples of the unsaturated amide compounds include acrylamide and methacrylamide. There is, but is not limited to this. These unsaturated monomers can be used individually or in mixture of 2 or more, respectively.

Specific examples of the copolymer of carboxyl group-containing ethylenically unsaturated monomers composed of such monomers include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / Benzyl methacrylate / 2-hydroxy ethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymer, and the like, but the present invention is not limited thereto. It is not.

The weight average molecular weight (Mw) of the copolymer of the ethylenically unsaturated monomer containing the carboxyl group is preferably 10,000 to 70,000, more preferably 20,000 to 50,000. The alkali-soluble resin is a factor that most influences the resolution of the pixel in the present invention. For example, in the case of the methacrylic acid / benzyl methacrylate copolymer, a result in which the resolution of the pixel is clearly changed by the acid value and the weight average molecular weight is obtained. For example, the best results were obtained when the content ratio of methacrylic acid / benzyl methacrylate was 25/75 (w / w) with an acid value of 80 to 120 mgKOH / g and a weight average molecular weight of 20,000 to 40,000. In addition, the said alkali-soluble resin can be used individually or in mixture of 2 or more types.

It is preferable that the usage-amount of the said alkali-soluble resin is 0.5-30 weight% with respect to the coloring photosensitive resin composition of this invention. If the content is less than 0.5% by weight, there is a problem that development does not occur in the alkaline developer, whereas if it exceeds 30% by weight, there is a disadvantage in that the surface smoothness is poor due to the lack of crosslinkability.

(C) photopolymerizable monomer

The photopolymerizable monomer used in the present invention is a monomer generally used in the color photosensitive resin composition for color filters, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1 , 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol Pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimetha Acrylate, propylene glycol dimethacrylate, 1,4-butane And the like come dimethacrylate, 1,6-hexanediol dimethacrylate.

It is preferable that the usage-amount of the said photopolymerizable monomer is 0.5-30 weight% with respect to the coloring photosensitive resin composition of this invention. If the content of the acrylic photopolymerizable monomer is less than 0.5% by weight, a problem occurs that the edges of the pattern are not formed cleanly, whereas if the content of more than 30% by weight is not developed in the alkaline developer, there are disadvantages in that stains or residues remain.

(D) photoinitiator

The photoinitiator used for this invention is a photoinitiator generally used for a coloring photosensitive resin composition, For example, 1 type from a triazine type compound, an acetophenone type compound, a benzophenone type compound, a thioxanthone type compound, and a benzoin type compound. The above may be selected, but is not necessarily limited thereto.

Specific examples of the triazine compound used as the photoinitiator include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2 -(3 ', 4'-dimethoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloro methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naph Sat 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-tri Azine, 2-4-trichloro methyl (piperonyl) -6-triazine, 2-4-trichloro methyl (4'-methoxy styryl) -6-triazine and the like.

Specific examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone and pt-butyltrichloro acetophenone , pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 3,3'-dimethyl-2-methoxy benzophenone, and 4,4 '. -Dichloro benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone and 2-chloro thi Orcanthones and the like.

As the benzoin-based compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like may be used.

It is preferable that the usage-amount of the said photoinitiator is 0.1 to 10 weight% with respect to the coloring photosensitive resin composition of this invention. If the content of the photopolymerization initiator is less than 0.1% by weight, photopolymerization does not occur sufficiently during exposure in the pattern forming process. On the other hand, if the content of the photopolymerization initiator is more than 10% by weight, the unreacted initiator remaining after the photopolymerization should decrease the transmittance.

(E) solvent

Solvents usable in the present invention include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like. It can be used or it can mix and use 2 or more types.

Although the usage-amount of the said solvent is not specifically determined, It is preferable to use about 20 to 90 weight% with respect to the coloring photosensitive resin composition of this invention.

Although the manufacturing method of the coloring photosensitive resin composition of this invention is not specifically limited, (1) The pigment (A-2) is a bead mill and a ball mill in the solvent (F) in which alkali-soluble resin (C) and a dispersing agent (B) are melt | dissolved. Obtaining a pigment dispersion through atomization of the pigment using a disperser such as a rod mill; (2) Add the pigment dispersion prepared in (1) to the solvent (F) in which the photopolymerizable monomer (D), the photopolymerization initiator (E), the alkali-soluble resin (C) and the coloring substance (A-1) are dissolved, and Mixing to obtain a colored photosensitive resin composition; And (3) using a prepared colored photosensitive resin composition using a suitable method such as spin coating, slit coating, etc. on the glass, to a thickness of 1.4 to 3.3㎛, developing and baking with exposure to light using ultraviolet light, alkaline developer By repeating the process according to the required number of R, G, B colors, it is possible to manufacture a color filter having a desired pattern. In the above process, crack resistance, solvent resistance and the like can also be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.

(F) other

The color filter photosensitive resin composition may further include a dispersant, a surfactant, and the like in addition to the components of the above (A) to (E).

As the dispersant, the pigment component is uniformly dispersed in the solvent, and any nonionic, anionic or cationic dispersant may be used.

Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxides Adducts, alkylamines and the like can be used, and specific examples thereof include BYPER's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK -165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, and DISPERBYK-2001; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 from EFKA Chemical; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000 and Solsperse 28000 from Zeneka; And PB711 and PB821 from Ajinomoto.

The dispersant may be included in an amount of 0.1 to 15% by weight based on the total amount of the colored photosensitive resin, and when the amount is less than 0.1% by weight, dispersion may be difficult or may be less stable. It may be difficult to form a pattern because it is not made.

In addition, the surfactant is a fluorine-based surfactant; Although silicone type surfactant etc. can be used, It is preferable to use a fluorine type surfactant.

The fluorine-based surfactant not only has excellent electrical characteristics, but also has high leveling property at high speed coating and less foaming due to fewer bubbles, so that the slit coating is a high speed coating method. ) Gives very good properties.

The fluorine-based surfactant may be made of polyether co-modified silicone, and specific examples thereof include FC-430, F-475, etc. of 3M, but are not particularly limited thereto. These may be used alone, but may be used by mixing two or more kinds.

The surfactant is preferably 0.01 to 5% by weight based on the total weight of the photosensitive resin composition for color filters, when using the surfactant in less than 0.01% by weight may not be easy to ensure the uniformity of coating as well as stains, 5 In the case where the content is used in an amount exceeding the wt%, the wetting property on the glass substrate may be deteriorated, and thus the coating may not be performed.

Moreover, the coloring photosensitive resin composition of this invention can also be manufactured by mixing a coloring agent (A), alkali-soluble resin (C), a photopolymerizable monomer (D), and a photoinitiator (E) at once.

Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples are for illustrative purposes only and are not to be construed as limiting the present invention.

A. Synthesis of Colored Materials

Synthesis Example 1

[Chemical Formula 5]

In a reactor equipped with a stirrer and a thermometer, 10 g of a phthaloquinoline chloride compound represented by Chemical Formula 5 (CI Pigment Yellow 138), 12 g of 2-mercaptoethane sulfonate, 8.5 g of sodium carbonate, and N, N'-dimethyl 250 g of midazolidone (DMI) were mixed and stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Then, the mixture was stirred at 190 ° C. for 8 hours to react. Then, the mixture was cooled to 90 ° C, suction filtered, and then the filtrate was poured into 700 g of acetone. Crystals were precipitated from the acetone solution, washed with acetone, filtered, and dried to obtain 8.1 g of a phthaloquinoline compound represented by the following formula (6).

[Formula 6]

Synthesis Example 2

5 g of the phthaloquinoline compound of Chemical Formula 6 obtained through Synthesis Example 1 was washed with water for 10 hours with 10% by weight aqueous hydrochloric acid and filtered, followed by N-methylpyrrole in which 2.3 g of 2-aminomethylpropanol was dissolved. Add to 200 g of money. After stirring at 50 ° C., the precipitate was precipitated using acetone, filtered and dried to obtain 4.89 g of a phthaloquinoline compound represented by Chemical Formula 7.

[Formula 7]

Synthesis Example 3

4.5 g of the phthaloquinoline compound represented by the following Chemical Formula 8 was obtained by using 1.9 g of t-butylamine instead of 2.3 g of 2-aminomethylpropanol as the amine salt in Synthesis Example 2.

[Formula 8]

Synthesis Example 4

In a reactor equipped with a stirrer and a thermometer, 9.7 g of phthaloquinoline chloride represented by Chemical Formula 5 of Synthesis Example 1, 13.8 g of 3-mercaptopropionic acid, 7.6 g of sodium carbonate, and N, N ' 200 g of dimethylimidazolidone (DMI) were mixed and stirred at 90 ° C. for 2 hours under a nitrogen atmosphere. Then, the mixture was stirred at 190 ° C. for 8 hours to react. Then, the mixture was cooled to 90 ° C., suction filtered, and then the filtrate was poured into 500 g of acetone. Crystals were precipitated from the acetone solution, washed with acetone, filtered, and dried to obtain 7.6 g of a phthaloquinoline compound represented by the following formula (9).

[Formula 9]

Synthesis Example 5

5 g of the phthaloquinoline compound of Chemical Formula 9 obtained in Synthesis Example 4 was added to 200 g of N-methylpyrrolidone in which 2-aminomethylpropanol was dissolved in excess, stirred at room temperature, and then precipitated using acetone. , Filtered and dried to obtain 4.2 g of a phthaloquinoline compound represented by the following formula (10).

[Formula 10]

Synthesis Example 6

[Formula 11]

8.5 g of diketopyrrolopyrrole compound represented by Chemical Formula 11 (CI Pigment Red 254), 11.5 g of 2-mercaptoethane sulfonate, 7 g of sodium carbonate, and N, N'-dimethylimide in a reactor equipped with a stirrer and a thermometer. 250 g of zolidon (DMI) were mixed and stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Then, the mixture was stirred at 190 ° C. for 8 hours to react. Then, the mixture was cooled to 90 ° C, suction filtered, and then the filtrate was poured into 500 g of acetone. Crystals were precipitated from the acetone solution, washed with acetone, filtered, and dried to obtain 6.7 g of a diketopyrrolopyrrole compound represented by the following formula (12).

[Formula 12]

Synthesis Example 7

[Formula 13]

8.5 g of indanthrone compound (CI Pigment Blue 60) represented by Chemical Formula 13, 13.2 g of 2-mercaptoethane sulfonate, 7.9 g of sodium carbonate, and N, N'-dimethylimidazoli in a reactor equipped with a stirrer and a thermometer. 300 g of DMI were mixed and stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Then, the mixture was stirred at 190 ° C. for 8 hours to react. Then, the mixture was cooled to 90 ° C., suction filtered, and then the filtrate was poured into 500 g of acetone. Crystals were precipitated from the acetone solution, washed with acetone, filtered, and dried to obtain 5.3 g of an indantron compound represented by the following formula (14).

[Formula 14]

Synthesis Example 8

[Formula 15]

11.5 g of a halogenated phthalocyanine compound represented by Chemical Formula 15 (CI Pigment Green 36), 24.5 g of 2-mercaptoethane sulfonate, 16.5 g of sodium carbonate, and N, N'-dimethylimidazolidone in a reactor equipped with a stirrer and a thermometer. 450 g of (DMI) were mixed and stirred at 160 ° C. for 4 hours under a nitrogen atmosphere. Then, the mixture was stirred at 190 ° C. for 8 hours to react. Then, the mixture was cooled to 90 ° C., suction filtered, and then the filtrate was poured into 1,500 g of acetone. Crystals were precipitated from the acetone solution, washed with acetone, filtered and dried to obtain 18.7 g of a halogenated phthalocyanine compound represented by the following formula (16).

[Formula 16]

B. Preparation of Pigment Dispersion

(Production Example 1)

Furtherance Content [g] Green pigment
(CI Pigment Green 36, Client) 150 Dispersant
PB821 (Ajinomoto Corporation) 30 Alkali soluble resin
Benzyl methacrylate / methacrylic acid copolymer (8/2 weight ratio)
Mw = 20,000 20 solvent
Propylene Glycol Methyl Ether Acetate (PGMEA) 800

After the green pigment is added to the solution in which the dispersant and the binder resin are dissolved in the solvent and stirred for 30 minutes, the mixture is placed in a circulating bead mill disperser having a chamber of 300 nm and dispersed for 2 hours. The dispersion was filtered through a 0.4 μm filter to give a green pigment dispersion having a pigment concentration of 15 wt% and a viscosity of 6.5 cP.

(Manufacture example 2)

As a yellow pigment (CI Pigment Yellow 138) instead of a green pigment, except that TDY2 (Dae Nippon Ink Chemical Co., Ltd.) was used in the same manner as in Preparation Example 1, the pigment concentration is 15% by weight, the viscosity is 10.5 cP A yellow pigment dispersion was prepared.

(Production Example 3)

In the same manner as in Preparation Example 1, except that IRGAPHOR RED BK-CF (Ciba Specialty, Inc.) was used as a red pigment (CI Pigment Red 254) instead of a green pigment, the pigment concentration was 15% by weight and the viscosity was 8.4. A red pigment dispersion, which is cP, was prepared.

(Production Example 4)

As a blue pigment (CI Pigment Blue 15: 6) instead of a green pigment, TDB2 (Dae Nippon Ink Chemical Co., Ltd.) and a purple pigment (CI Pigment Violet 23), Hostaperm ^® Violet RL- ED LV 3064 (Client) 80:20 A blue pigment dispersion having a pigment concentration of 15% by weight and a viscosity of 11.2 cP was prepared except that it was used as a ratio of (weight ratio).

C. Preparation of Colored Photosensitive Resin Composition

(Examples and Comparative Examples)

The colored photosensitive resin composition of Examples 1-10 and Comparative Examples 1-3 was prepared with the composition of Table 1 below.

TABLE 1

The coloring photosensitive resin composition using the said components is manufactured by the following method.

(A) The colored material prepared through Synthesis Example was dissolved in N-methylpyrrolidone and stirred for 1 hour.

(B) After dissolving the photopolymerization initiator in PGMEA and ethyl propionate, the mixture was stirred at room temperature for 2 hours, an alkali-soluble resin and a photopolymerizable monomer were added, and the mixture was stirred at room temperature for 2 hours.

(C) After mixing (A) and (B), the pigment dispersion prepared in Preparation Example was added and stirred at room temperature for 1 hour.

(D) As the surfactant, a fluorine-based surfactant (F-475, DIC Corporation) was added and stirred at room temperature for 1 hour.

(E) Three times of filtration was performed to remove impurities.

D. Manufacturing of color filter

The colored photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 prepared as described above were prepared on a 8 cm × 8 cm glass substrate using a spin-coater (K-Spin8, KDNS).

2.5 Apply to a thickness of μm and dry for 110 seconds on a hotplate at 100 ° C. Then, using a mask and an exposure machine (Nikon, I10C) engraved with a pattern of various sizes was exposed at 60 mJ / ㎠, and developed at 25 ℃ 1% aqueous solution of KOH, after washing the developed substrate 230 The color filter was formed by forming a color filter pattern by drying in an oven at 30 ° C. for 30 minutes.

E. Color Characteristic Evaluation

Measurement of the CIE chromaticity coordinates (x, y, Y) of the color filters manufactured using the Examples 1 to 10 and Comparative Examples 1 to 3 was measured using a color spectrophotometer (MCPD3000, Otsuka Electronics).

Contrast ratio value is measured by placing a sample between two polarizing films using a contrast tester (Contrast tester CT-1, Tsubosaka Co., Ltd.) with polarizers installed on the upper and lower layers. The ratio of the values at the time of being measured was shown in Table 2 below. 1 shows spectral spectra showing the transmittances of Example 6 and Comparative Example 1. FIG. Looking at Figure 1, it can be seen that the transmittance of the color filter according to Example 6 in the wavelength region of 660 to 780 nm is excellent. Thus, when using a small amount of the phthaloquinoline compound according to the formula 10 of the present invention as a colorant shows a better transmittance than using a large amount of pigment dispersion of the same color can be seen in Figure 1, as shown in the results of Table 2 It can be seen that the Y value is 1.2 higher.

F. Reliability Assessment

After drying for 2 hours in an oven at 230 ℃ for heat resistance measurement, the degree of change in the initial chromaticity coordinate value was confirmed. When the rate of change of the initial chromaticity coordinate value is less than 3, it is represented by ◎, less than 6 by ○, and by 6 or more by x.

In addition, the light resistance was measured by using a light resistance tester (Xenon Arc Fade-O-Meter, Atlas) for 50 hours in a Xenon-Arc lamp of 150 W / m ² , and then confirmed the degree of change. When the rate of change of the initial chromaticity coordinate value is less than 3, it is indicated by ◎, by 3 or more and by less than 6 by ○, and by 6 or more by X.

TABLE 2

Color characteristic evaluation result Reliability Evaluation Results x y Y Contrast Ratio Heat resistance Light resistance Example 1 0.521 0.315 73.1 6,200 ○ ◎ Example 2 0.521 0.316 73.2 6,400 ◎ ◎ Example 3 0.521 0.319 73.6 6,500 ○ ◎ Example 4 0.521 0.318 73.5 6,700 ○ ◎ Example 5 0.521 0.316 73.2 6,500 ◎ ◎ Example 6 0.521 0.319 73.8 7,100 ◎ ○ Example 7 0.521 0.316 73.1 7,300 ◎ ◎ Example 8 0.586 0.320 26.2 6,200 ◎ ◎ Example 9 0.588 0.320 26.3 6,300 ◎ ○ Example 10 0.141 0.078 8.8 7,200 ◎ ◎ Comparative Example 1 0.521 0.316 72.6 5,200 ◎ ◎ Comparative Example 2 0.585 0.320 25.8 5,400 ◎ ◎ Comparative Example 3 0.141 0.077 8.6 6,500 ○ ○

As shown in Table 2, the color filters of Examples 1 to 10 according to the present invention have heat resistance and light resistance higher than required levels, and comparing Examples and Comparative Examples of the same color, Examples 1 to 10 of the present invention. It can be seen that the luminance (Y) and contrast ratio of the color filter according to the superior to Comparative Examples 1 to 3.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

1 is a spectral spectrum showing the transmittances of Example 6 and Comparative Example 1. FIG.

Claims (5)

coloring agent; Alkali-soluble resins; Photopolymerizable monomers; Photopolymerization initiator; And solvents, The coloring agent is a coloring photosensitive resin composition comprising a pigment and at least one coloring material selected from the group consisting of compounds of the following formulas (1) to (4). [Formula 1]

(In the formula 1, And, ^- X ₁ and X ₂ are the same as or different from each other, and, independently, SO ₃ ^- or COO Y ₁ and Y ₂ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula A, B is a halogen element, n ₁ and n ₂ are each independently an integer of 1 to 4, m ₁ and m ₂ are each independently an integer of 1 to 4, k ₁ and k ₂ are each independently an integer of 0 to 3, m ₁ + k ₁ = m ₂ + k ₂ = 4) [Formula 2]

(3)

(In Chemical Formulas 2 and 3, And, ^- X ₃ to X ₆ and is the same as or different from each other, each independently, SO ₃ ^- or COO Y ₃ to Y ₆ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula (A), n ₃ to n ₆ are each independently an integer of 1 to 4, m ₃ to m ₆ are each independently 0 to 1, m ₃ + m ₄ ≥ 1 and m ₅ + m ₆ ≥ 1) [Formula 4]

(In Formula 4, And, ^- X ₇ to X ₁₀ are the same as or different from each other, and, independently, SO ₃ ^- or COO Y ₇ to Y ₁₀ are the same as or different from each other, and each independently, H ⁺ ; Cations of alkali metals; And it is selected from the group consisting of ammonium ions represented by the formula (A), B is a halogen element, n ₇ to n ₁₀ are each independently an integer of 1 to 4, m ₇ to m ₁₀ are each independently 0 to 1, m ₇ + m ₈ + m ₉ + m ₁₀ ≥ 1, k ₇ to k ₁₀ are each independently an integer of 0 to 3, m ₇ + k ₇ = m ₈ + k ₈ = m ₉ + k ₉ = m ₁₀ + k ₁₀ = 4) [Formula A]

(In Formula A, R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted group Substituted alkynyl groups having 2 to 30 carbon atoms, substituted or unsubstituted oxyalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or Unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkenyl groups having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms 2 to 30 30 heteroalkynyl groups, substituted or unsubstituted heterooxyalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted carbon It can be selected from 1 to 30 hetero aryl group, hetero aralkyl, and derivatives thereof or polymers of a substituted or unsubstituted C2 to 30 in.) The method of claim 1, The colored photosensitive resin composition, 1 to 40 wt% colorant; 0.5-30 wt% of alkali-soluble resin; 0.5-30 wt% of the photopolymerizable monomer; 0.1 to 10 wt% photopolymerization initiator; And Solvent Residue Colored photosensitive resin composition comprising a. The method of claim 1, The colorant, Coloring photosensitive resin composition is one or more coloring materials selected from the group consisting of Formulas 1 to 4 contained in 5 to 100 parts by weight based on 100 parts by weight of the pigment. The method of claim 1, The colored photosensitive resin composition further comprises at least one additive selected from the group consisting of dispersants and surfactants. The color filter manufactured using the coloring photosensitive resin composition of any one of Claims 1-4.

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