KR20100072934A - Photosensitive resin composition for color filter and color filter using same - Google Patents

Abstract

PURPOSE: A photoresist resin composition for a color filter, and the color filter using thereof are provided to manufacture the high definition color filter with the uniform thickness of a film, and to secure the excellent dispersion stability of a pigment, and the mobility. CONSTITUTION: A photoresist resin composition for a color filter contains the following: a dispersion resin selected from an unsaturated ethylene oligomer marked with chemical formula 1 or its homopolymer, or the unsaturated ethylene oligomer and an unsaturated ethylene monomer copolymer; an acrylic binder resin containing a carboxy group; a photo-polymerizable monomer; a photopolymerization initiator; and a pigment and a solvent. In the chemical formula 1, R1 and R1` are aliphatic hydrocarbon groups of C1~C4, respectively. R2 and R2` are hydrogen atoms or methyl groups, respectively.

Description

Photosensitive resin composition for color filters and color filter using same {PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER AND COLOR FILTER USING SAME}

The present invention relates to a photosensitive resin composition for a color filter and a color filter using the same. More particularly, the present invention relates to a color filter having a high dispersion stability, high color reproducibility, and excellent fluidity. It relates to the photosensitive resin composition for color filters that can be produced.

As the recent spread of digital cameras and large-screen liquid crystal display devices has increased, there is a growing demand for new performance enhancements for liquid crystal display devices. The liquid crystal display reproduces various images of light passing through a pair of polarizing plates facing each other with a liquid crystal between them by color filters made of three primary color pixels of red, green, and blue. Various colors are reproduced, from an image representing white that is transmitted as much as possible to an image representing black that does not block and transmit all light.

In the liquid crystal display, it is required to improve the luminance Y of the white display color filter in order to improve the power consumption. However, if the luminance Y is improved, the color reproducibility of the color filter is lowered. In order to solve this problem, it is inevitably required to increase the fineness and concentration of the pigment used as a colorant, but if the particle size of the pigment is increased to increase the brightness of the image or the content is increased to increase the color reproducibility, the dispersion stability and fluidity There is a known problem that it is difficult to form a uniform coating film at the time of coating apart and the brightness of the image is not uniform. Conventional coating methods commonly used in the photosensitive composition for color filters include a central drop coating method, a slit end spin coating method and a slit coating method. Non-Newtonian Fluids (Non-Newtonian Fluids) is a film thickness between the center and the distal end when the coating is applied, causing unevenness or color difference of the pixel. In order to solve such a problem, the refinement and stability of the pigment is important. For this purpose, it is important to select a dispersion resin having excellent dispersion efficiency and have a close relationship with the performance of the color filter according to the structure and type of the dispersion resin. Japanese Patent Application Laid-Open No. 8-259876 discloses a photosensitive composition for color filters prepared from a pigment dispersion liquid having a small particle size and excellent dispersion stability using a copolymer containing unsaturated ethylene, but is dispersed as the pigment concentration increases. There is a disadvantage of poor efficiency. In addition, Japanese Patent Application Laid-Open No. 9-146272 discloses a composition in which the pigment is micronized using a graft copolymer containing an acidic group as a functional group adsorbed to the pigment, but as the concentration of the pigment increases, the graft chain Problem of deterioration of dispersion stability due to deterioration of the three-dimensional repulsion effect, and in the case of Japanese Patent Application Laid-Open No. 10-339949, the adsorption of the pigment is increased by using a copolymer containing nitrogen atoms in the polymer backbone, Due to the increase in dispersion stability due to, there is a problem that the post-exposure phenomenon is not made smoothly.

The present invention is to provide a photosensitive resin composition for a color filter which can produce a high resolution color filter having a high dispersion stability and color reproducibility of pigments and excellent fluidity and uniform film thickness.

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

According to one embodiment of the present invention, (A) an unsaturated ethylene oligomer represented by the following formula (1), a homopolymer thereof, or a dispersion resin which is a copolymer of the unsaturated ethylene oligomer and an ethylenically unsaturated monomer, (B) a carboxyl group-containing acrylic binder It provides the photosensitive resin composition for color filters containing resin, (C) photopolymerizable monomer, (D) photoinitiator, (E) pigment, and (F) solvent.

[Formula 1]

(In the formula 1,

R ₁ and R ₁ ′ are the same or different from each other, and each independently, a C ₁ to C ₄ aliphatic hydrocarbon group,

R ₂ and R ₂ ′ are the same or different from each other and are each independently a hydrogen atom or a methyl group,

A ₁ is a copolymerization functional group including a repeating unit of Formula 2 and a repeating unit of Formula 3.

[Formula 2]

(3)

(In Chemical Formulas 2 and 3,

X ₁ and X ₁ ′ are the same or different from each other and are each independently residues of an aliphatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, or a combination thereof;

Y ₁ and Y ₁ ′ are the same or different from each other and are each independently residues of a polyhydric alcohol, and at least one of Y ₁ and Y ₂ comprises an ionic group.)

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

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

The photosensitive resin composition according to the present invention has a high dispersion stability and color reproducibility of the pigment, excellent fluidity, excellent color characteristics and contrast ratio, and may be usefully used for manufacturing a color filter having a uniform film thickness.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise specified herein, an "alkyl group" means an alkyl group having 1 to 20 carbon atoms, an "aryl group" means an aryl group having 6 to 30 carbon atoms, and a "cycloalkyl group" means a cycloalkyl group having 3 to 20 carbon atoms. The term "aliphatic hydrocarbon group" means an alkyl group having 1 to 24 carbon atoms, an alkylene group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkenylene group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, or carbon atoms. It means an alkynylene group of 2 to 24, and an "aromatic hydrocarbon group" means an aryl group having 6 to 20 carbon atoms.

The photosensitive resin composition for color filters according to the embodiment of the present invention is a dispersion resin which is (A) an unsaturated ethylene oligomer, a homopolymer thereof, or a copolymer of the unsaturated ethylene oligomer and another ethylenically unsaturated monomer (B) carboxyl group-containing acrylic vine Furthermore, it contains resin, (C) photopolymerizable monomer, (D) photoinitiator, (E) pigment, and (F) solvent.

Hereinafter, each component included in the photosensitive resin composition for color filters according to the embodiment of the present invention will be described in detail.

(A) Dispersion Resin

The dispersion resin is preferably an unsaturated ethylene oligomer represented by the following formula (1), a homopolymer thereof, or a copolymer of the unsaturated ethylene oligomer and the ethylenically unsaturated monomer.

[Formula 1]

(In the formula 1,

R ₁ and R ₁ ′ are the same or different from each other, and each independently, a C ₁ to C ₄ aliphatic hydrocarbon group,

R ₂ and R ₂ ′ are the same or different from each other and are each independently a hydrogen atom or a methyl group,

A ₁ is a copolymerization functional group including a repeating unit of Formula 2 and a repeating unit of Formula 3.

[Formula 2]

(3)

(In Chemical Formulas 2 and 3,

X ₁ and X ₁ ′ are the same or different from each other and are each independently residues of an aliphatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, or a combination thereof;

Y ₁ and Y ₁ ′ are the same or different from each other and are each independently residues of a polyhydric alcohol, and at least one of Y ₁ and Y ₂ comprises an ionic group.)

At this time, the ionic group is preferably COOH or salts thereof.

Preferably, A ₁ in Formula 1 may be a structure including a urethane group produced by the reaction of a compound having a diisocyanate group and a polyhydric alcohol including at least one ionic group.

In addition, in Formulas 2 and 3, X ₁ and X ₁ ′ are hexamethylene group, toluene group, diphenylmethylene group, 2,2,4-trimethylhexamethylene group, p-phenylene group, 4,4-dicyclohexyl Methylene group, m-xylene group, naphthalene group, cyclohexylene group, isopron group, etc. are mentioned, but it is not limited to this. Preferably, aromatic diisocyanate compounds such as toluene group, xylene group, naphthalene group and the like may be further preferred in terms of improving the dispersibility of the pigment. 　　

In addition, in Formulas 2 and 3, at least one of Y ₁ and Y ₁ ′ includes an ionic group, and the ionic group preferably includes at least one structure of Formulas 4 to 6 below.

[Formula 4]

[Chemical Formula 5]

[Formula 6]

(In Chemical Formulas 4 to 6,

R ₃ and R ₃ ′ are the same or different from each other and are each independently an aliphatic hydrocarbon group,

R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, preferably a methyl group,

R ₅ , R ₆ and R ₇ are the same or different and are each independently a hydrogen atom, an aliphatic hydrocarbon group of C ₁ to C ₂₄ , or an aromatic hydrocarbon group of C ₆ to C ₂₀ ,

M is a monovalent metal, preferably Li, Na or K.)

When at least one of Y ₁ and Y ₂ is derived from a polyhydric alcohol comprising an ionic group, the other one may be derived from a polyhydric alcohol containing no ionic group. Representative examples of the polyhydric alcohol not containing an ionic group include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polybutadiene diol, Glycols such as polytetramethylene glycol and polycaprolactone diol; Or alcohol amines such as dimethylaminopropanediol, methyl diethanolamine, dimethyl diethanolamine, butyl diethanolamine and methyldiisophoropanolamine. As the amount of ethylene oxide increases, it is advantageous to the developing process, but when too much added glycol is used, it may not be dissolved in the solvent in preparing the composition.

Other ethylenically unsaturated monomers copolymerizable with the unsaturated ethylene oligomer represented by Formula 1 include alkenyl aromatic monomers; Unsaturated carboxylic acid esters; Unsaturated carboxylic acid amino alkyl esters, carboxylic acid vinyl esters, unsaturated carboxylic acid glycidyl esters, vinyl cyanide compounds, unsaturated amides, combinations thereof and the like can be used.

Specific examples of the ethylenically unsaturated monomers include alkenyl aromatic monomers such as styrene, α-methyl styrene, vinyltoluene, vinyl benzyl methyl ester, and vinyl benzyl methyl ether; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylic Unsaturated carboxylic acid esters such as latex, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate; Unsaturated carboxylic acid amino alkyl esters such as 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate and 2-dimethyl amino ethyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amides, such as acryl amide and methacryl amide, a mixture thereof, etc. can be used. In addition, a copolymer containing an unsaturated ethylene oligomer represented by the formula (1) may be used.

When the dispersion resin is a copolymer, the unsaturated ethylene oligomer represented by Formula 1 may be included in 10 to 40% by weight, preferably 5 to 20% by weight relative to the total copolymer.

The dispersion resin preferably has a weight average molecular weight (Mw) of 10,000 to 70,000. Within this range, the pigment dispersion has an appropriate viscosity and has excellent dispersibility.

The dispersion resin is preferably contained in 0.5 to 5% by weight based on the total amount of the photosensitive resin composition. When the content of the dispersion resin is in the above range, the dispersion stability and color reproducibility of the pigment are high, and thus the fluidity is excellent, which is preferable. 　　

(B) carboxyl group-containing acrylic binder resin

The carboxyl group-containing acrylic binder resin is a copolymer of an ethylenically unsaturated first monomer having at least one carboxyl group and another ethylenically unsaturated second monomer copolymerizable therewith.

At this time, the carboxyl group-containing ethylenically unsaturated first monomer is in the range of 10 to 40% by weight, preferably 20 to 30% by weight based on the total copolymer.

Examples of the carboxyl group-containing ethylenically unsaturated first monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like, but are not limited thereto. The carboxyl group-containing acrylic binder resin used in the present invention contains at least one first monomer thereof.

As another ethylenically unsaturated 2nd monomer copolymerizable with the said carboxyl group-containing ethylenically unsaturated monomer, For example, Styrene, such as styrene and (alpha) -methyl styrene; Vinyltoluene; Vinyl benzyl methyl ether; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylic Unsaturated carboxylic acid esters such as latex, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate; Unsaturated carboxylic acid amino alkyl esters such as 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate and 2-dimethyl amino ethyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amides such as acryl amide and methacryl amide, and the like, and the like, but are not limited thereto. The said carboxyl group-containing acrylic binder resin contains 1 or more types of 2nd monomers among these.

Specific examples of the carboxyl group-containing acrylic binder resin composed of monomers as described above include methacrylic acid / methyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene Copolymers, methacrylic acid / benzyl methacrylate / 2-hydroxy ethyl methacrylate copolymers, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymers; It is not limited to this.

The carboxyl group-containing acrylic binder resin preferably has a weight average molecular weight (Mw) of 10,000 to 70,000, and more preferably has a weight average molecular weight of 20,000 kPa to 50,000. When the weight average molecular weight is in the above range, it is preferable because it is excellent in developability with respect to the alkaline developer and can stabilize the pigment dispersion.

As for the acid value of the said carboxyl group-containing acrylic binder resin, it is more preferable that it is 20-60 mgKOH / g. In the said range, since developability is excellent and the storage stability of an ink composition can be improved, it is preferable.

The carboxyl group-containing acrylic binder resin is preferably contained in 0.5 to 30% by weight based on the total amount of the photosensitive resin composition. When the content of the binder resin is less than 0.5% by weight, a problem may occur in which the developer is not developed in an alkaline developer. When the content of the binder resin is more than 30% by weight, crosslinkability may be insufficient and the surface smoothness may be deteriorated.

The carboxyl group-containing acrylic binder resin is a factor which has the greatest influence on the resolution of pixels in the present invention. For example, when the carboxyl group-containing acrylic binder resin is a methacrylic acid / benzyl methacrylate copolymer, a result in which the resolution of the pixel is clearly changed by acid value and molecular weight is obtained. For example, when the content ratio of methacrylic acid / benzyl methacrylate is 25/75% by weight of the acid value of 80 to 120 mgKOH / g, the weight average molecular weight 20,000 to 40,000 was the best results. In addition, the said alkali-soluble resin can be used individually or in mixture of 2 or more types.

(C) photopolymerizable monomer

The photopolymerizable monomer is a monomer generally used in the photosensitive resin composition for color filters, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexane Diol 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 dimethacrylate, propylene Glycoldimethacrylate, 1,4-butanedioldimethacrylate, 1,6-hex Diol dimethacrylate, but include methacrylate and so on, and the like.

The photopolymerizable monomer is preferably included in 0.5 to 30% by weight based on the total amount of the photosensitive resin composition. If the content of the photopolymerizable monomer is less than 0.5% by weight, a problem may occur in that the corners of the pattern are not formed cleanly. When the content of the photopolymerizable monomer is greater than 30% by weight, the developer may not be developed in the alkaline developer, or stains or residues may remain. Not desirable

(D) photoinitiator

The photopolymerization initiator is a photopolymerization initiator generally used in the photosensitive resin composition, for example, a triazine compound, acetophenone compound, benzophenone compound, thioxanthone compound, benzoin compound, oxime compound and the like can be used. have.

Specific examples of the triazine-based compound 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 (trichloromethyl) -s-tri Azine, 2- (p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-tri Azine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl)- 4,6-bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 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'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-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, 4,4'-bis (dimethyl amino) benzophenone, and 4,4-dimethyl. Aminobenzophenone, 4,4'-bis (diethyl amino) benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone and 2-chloro thi Orcanthone etc. are mentioned.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred as the photopolymerization initiator.

In addition to the photopolymerization initiator, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, and the like can also be used as the photopolymerization initiator.

The photopolymerization initiator is preferably included in 0.1 to 10% by weight based on the total amount of the photosensitive resin composition. If the content of the photopolymerization initiator is less than 0.1% by weight, photopolymerization does not occur sufficiently during exposure in the pattern formation process, whereas if it exceeds 10% by weight, a problem may occur in that the unreacted initiator remaining after photopolymerization lowers the transmittance.

(E) pigment

The pigment may be a pigment having a color of red, green, blue, yellow, violet. Specific examples include organic pigments such as condensed polycyclic pigments such as anthraquinone pigments and perylenes, phthalocyanine pigments and azo pigments; Or inorganic pigments, such as carbon black, can be used, These pigments can be used individually or in mixture of 2 or more types, respectively.

In addition, the pigment may be used by adjusting the primary particle size small. As a method of controlling the primary particle size of the pigment small, a method of mixing the water-soluble inorganic salt and the humectant, kneading and refining in a high pressure kneader to adjust the size of the primary particles to less than 70 nanometers, sulfuric acid and The acid pasting method of dissolving in the same acid and re-precipitating again in a poor solvent to obtain small particles, or the method of adjusting the primary particle size to a small size by dry grinding the pigment for a long time using a high-speed sand mill, etc. In addition, it can be used in other ways to adjust the primary particle size small.

It is also possible to use commercially available pigments by reducing the size of the primary particles.

The pigment preferably has an average particle diameter (D50) of 30 to 70 nanometers. If the average particle diameter of the pigment is less than 30 nanometers, problems such as heat resistance, chemical resistance, adhesion, etc. may occur after pixel formation, and if it exceeds 100 nanometers, the brightness may fall, which is not preferable.

The pigment is preferably included in 0.1 to 40% by weight based on the total amount of the photosensitive resin composition. When the content of the pigment is less than 0.1% by weight, the coloring effect is insufficient and the color reproducibility is low, and when it exceeds 40% by weight, the developability is lowered and the stability is not preferable, which is not preferable.

(F) solvent

Examples of the solvent include ethylene glycols such as ethyl 3-ethoxy propionate, ethylene glycol, diethylene glycol and polyethylene glycol; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol; Propylene glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether and dipropylene glycol diethyl ether Ethers; Propylene glycol ether acetates such as propylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; Amides such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide; Ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone; Petroleum such as toluene, xylene and solvent naphtha; Esters such as ethyl acetate, butyl acetate and ethyl lactate; And those selected from the group consisting of mixtures.

The solvent may be included in the amount of the remainder in the photosensitive resin composition, preferably from 20 to 90% by weight based on the total amount of the photosensitive resin composition. When the content of the solvent is within the above range, the coating property of the photosensitive resin composition is excellent, and flatness can be maintained in a film having a thickness of 3 µm or more, which is preferable.

(G) other additives

The color filter photosensitive resin composition may further include a surfactant and the like in addition to the components of A) to F).

As the surfactant, F-475 (DIC) or the like may be used, but is not limited thereto.

In addition, the photosensitive resin composition may further include an epoxy compound as needed for the improvement of adhesion and other properties. The epoxy compound is selected from the group consisting of epoxy novolac acrylic carboxylate resin, ortho cresol novolac epoxy resin, phenol novolac epoxy resin, tetramethyl bi-phenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin 1 or more types can be used. The content of the epoxy compound is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the content of the epoxy compound is included in the range of 0.01 to 5 parts by weight, it is preferable because the adhesion and other properties can be improved in storage and economically.

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

As an example of the manufacturing method of the photosensitive resin composition which has the above structure, (A) dispersion which is an unsaturated ethylene oligomer represented by following General formula (1), its homopolymer, or the copolymer of the said unsaturated ethylene oligomer and ethylenically unsaturated monomer. Pigment (E) is added to a medium in which the resin and the solvent are mixed, and the pigment is refined by using a bead mill, a ball mill, a rod mill, or the like to prepare a pigment dispersion, and the pigment dispersion (B) is a carboxyl group-containing acrylic binder resin. And (C) photopolymerizable monomer, (D) photoinitiator, (F) solvent, and the method of mixing (G) other additives are mentioned. However, the present invention is not limited thereto, and (A) an unsaturated ethylene oligomer represented by Formula 1 below, a homopolymer thereof, or a dispersion resin which is a copolymer of the unsaturated ethylene oligomer and an ethylenically unsaturated monomer, and (B) a carboxyl group-containing acrylic binder resin , (C) photopolymerizable monomer, (D) photopolymerization initiator, (F) solvent, and (G) other additives are all mixed together to produce a method.

According to another embodiment of the present invention provides a color filter manufactured using the photosensitive resin composition having the above configuration.

The photosensitive composition of this invention is apply | coated on the glass in thickness of 1.4-3.3 micrometers using suitable methods, such as spin coating and slit coating. After the application, ultraviolet light is irradiated to form a pattern necessary for the color filter, and then the application layer is treated with an alkaline developer to dissolve the unilluminated portion of the application layer and form a pattern for the image color filter. By repeating this process in accordance with the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

Synthesis Example 1

348 g of toluene diisocyanate (TDI) was added to a four-necked flask equipped with a cooler and a stirrer, and nitrogen gas was flowed for 10 minutes to remove water, followed by 100 g of dimethylolpropionic aicd (DMPA) and dibutyl tin di. A solution of 1.5 g of laurate (DBTDL) dissolved in 300 g of dimethyl acetate (DMAc) was slowly added and stirred at room temperature of 25 ° C. for 30 minutes, and the reaction temperature was raised to 80 ° C. for 4 hours. Subsequently, 500 g of polyethylene glycol having a weight average molecular weight of 400 was slowly added to the reaction product. Subsequently, 1.0 g of dibutyltin dilaurate (DBTDL) and 260 g of hydroxyethylmethacrylate (HEMA) were added to a solution dissolved in dimethyl acetate (DMAc), followed by stirring at 45 ° C. for 12 hours. 50 g of triethylamine was added thereto, followed by stirring at room temperature for 1 hour to prepare an unsaturated ethylene oligomer including an amine salt.

Synthesis Example 2

348 g of toluene diisocyanate (TDI) was added to a four-necked flask equipped with a cooler and a stirrer, and water was removed by flowing nitrogen gas for 10 minutes, followed by 100 g of dimethylolpropionic aicd (DMPA) and dibutyl tin dilau A solution of 1.5 g of latex (DBTDL) dissolved in 300 g of dimethyl dimethyl acetate (DMAc) was added slowly at 30 ° C. for 30 minutes and stirred. The reaction temperature was raised to 80 ° C. for 4 hours, and the reaction temperature was 45 After reducing to ℃ ℃ 300g of polyethylene glycol having a molecular weight of 600 was slowly added to react for 3 hours to obtain a reaction product. The reaction product thus obtained was added to a solution of 1.0 g of dibutyl tin dilaurate (DBTDL) and 260 g of hydroxyethyl methacrylate in dimethyl acetate (DMAc), followed by stirring at 45 ° C. for 12 hours to prepare an unsaturated ethylene oligomer.

≪ Synthesis Example 3 &

444.5 g of isophorone diisocyanate (IPDI) was added to a four-necked flask equipped with a cooler and a stirrer, and nitrogen gas was flowed for 10 minutes to remove water, followed by 100 g of dimethylolpropionic aicd (DMPA). And dibutyltin dilaurate (DBTDL) 1.5g dissolved in 300g of dimethyl acetate (DMAc) was slowly added and stirred for 30 minutes at 25 ℃ room temperature, the reaction temperature was raised to 80 ℃ to react for 4 hours. . Subsequently, 500 g of polypolytetramethylene glycol having a weight average molecular weight of 1,000 was slowly added to the reaction product to react. Thereafter, the reaction product was added to a solution in which 1.0 g of dibutyl tin dilaurate (DBTDL) and 260 g of hydroxyethyl methacrylate were dissolved in demethyl acetate (DMAc), followed by stirring at 45 ° C. for 12 hours to prepare an unsaturated ethylene oligomer. .

<Manufacture example 1>

2,2-azobis (2,4-dimethylvaleronitrile) in a four-necked flask equipped with a cooler and a stirrer 　 A solution in which 2.3 g was dissolved in 400 g of propylene glycol monomethyl ether acetate (PGMEA), 15 g of unsaturated ethylene oligomer containing amine salt prepared in Synthesis Example 1, 20 g of methacrylic acid, and 65 g of benzyl methacrylate were added, and the inside of the flask was added. Substituted with nitrogen and slowly warmed to 80 ° C., the polymerization was carried out for 8 hours. Thereafter, the mixture was heated to 100 ° C., further added 0.7 g of 2,2-azobis (2,4-dimethylvaleronitrile), and further polymerized for 1 hour to prepare a dispersion resin having a solid content of 33.3 wt%. It was confirmed using gel chromatography (GPC) that the weight average molecular weight (Mw) of this dispersion resin was 21,000.

<Manufacture example 2>

Except for changing the unsaturated ethylene oligomer prepared in Synthesis Example 1 to the unsaturated ethylene oligomer prepared in Synthesis Example 2 was carried out in the same manner as in Preparation Example 1 to prepare a dispersion resin having a solid content of 35.6% by weight. It was confirmed using gel chromatography (GPC) that the weight average molecular weight (Mw) of this dispersion resin was 27,000.

<Manufacture example 3>

Except for changing the unsaturated ethylene oligomer prepared in Synthesis Example 1 to the unsaturated ethylene oligomer prepared in Synthesis Example 3 was carried out in the same manner as in Preparation Example 1 to prepare a dispersion resin having a solid content of 37.8% by weight. It was confirmed using gel chromatography (GPC) that the weight average molecular weight (Mw) of this dispersion resin was 29,000.

&Lt; Example 1 >

90 g of green pigment (PG36, manufactured by Clariant, trade name 8G) and 60 g of yellow pigment (PY138, manufactured by Nippon Nippon Ink Chemical Co., Ltd., brand name TDY2), 35 g of the dispersion resin prepared in Preparation Example 1, and 30 g of PB821 (manufactured by Ajinomoto Co., Ltd.) The solution dissolved in 795 g of propylene glycol methyl ether acetate was added and stirred for 30 minutes. Subsequently, the agitated material was placed in a circulating bead mill disperser having a chamber of 300 ml and dispersed for 2 hours, and filtered through a 0.4 micron filter to prepare a pigment dispersion having a pigment concentration of 15% by weight.

<Example 2>

A pigment dispersion was prepared in the same manner as in Example 1 except that the dispersion resin was changed to the dispersion resin prepared in Preparation Example 2.

<Example 3>

A pigment dispersion was prepared in the same manner as in Example 1 except that the dispersion resin was changed to the dispersion resin prepared in Preparation Example 3.

Comparative Example 1

A pigment dispersion was prepared in the same manner as in Example 1 except that a copolymer of benzyl methacrylate and methacrylic acid (8: 2) was used as the dispersion resin.

[Physical Evaluation 1]

Fluidity Evaluation of Pigment Dispersions

The viscosity of the pigment dispersions obtained in Examples 1 to 3 and Comparative Example 1 was measured at 25 ° C. at 5 rpm and 20 rpm using a viscometer (Brookfield Co., Ltd.-DVIII DVUltra). The fluidity parameters were defined as follows, and the measurement results are shown in Table 1.

[Equation 1]

Flow parameter = viscosity at 5 rpm / viscosity at 20 rpm

TABLE 1

If the fluidity parameter is large, there is a tendency that the difference in the film thickness of the central portion and the end portion is large, which may cause a problem of color difference in the manufacturing of color filters. Low value was confirmed.

<Example 4>

(A ') 47.4 g of the pigment dispersion prepared in Example 1

(B) 5 g of carboxyl group-containing acrylic binder resin

Methacrylic acid / benzyl methacrylate = 25/75 (% by weight), weight average molecular weight (Mw) = 25,000

(C) photopolymerizable monomer

Dipentaerythritol hexaacrylate (DPHA) 4.1g

(D) photoinitiator

TPP 0.2g

(F) solvent 　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　

Propylene Glycol Methyl Ether Acetate 19.4g

23.8 g of ethyl 3-ethoxy propionate

(G) other additives

0.1 g of F-475 (fluorine-based surfactant)

The photosensitive resin composition was manufactured by the following method using the component of said (A)-(G).

After dissolving a photoinitiator in a solvent, it stirred at room temperature for 2 hours. Subsequently, the carboxyl group-containing acrylic binder resin and the photopolymerizable monomer were added and stirred at room temperature for 2 hours. To this, a pigment dispersion was added and stirred at room temperature for 1 hour. Thereafter, the mixture was filtered three times to obtain a photosensitive resin composition from which impurities were removed.

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 4 except that the pigment dispersion was changed to the pigment dispersion prepared in Example 2.

<Example 6>

A photosensitive resin composition was prepared in the same manner as in Example 4 except that the pigment dispersion was changed to the pigment dispersion prepared in Example 3.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 4 except that the pigment dispersion was changed to the pigment dispersion prepared in Comparative Example 1.

[Physical Evaluation 2]

Developing time measurement

The photosensitive resin compositions prepared in Examples 4 to 6 and Comparative Example 2 were applied to a glass of 8 cm × 8 cm using a spin coater, dried at 100 ° C. for 110 seconds, and then exposed using a mask engraved with patterns of various sizes. Thereafter, the solution was developed with a 1.5 wt% KOH solution at 25 ° C., and development times are shown in Table 2. The developed substrate was washed and then dried in an oven at 230 ° C. for 30 minutes to produce a “monochrome coated” color filter. At this time, the developing time was measured by the time when all the non-exposed part melt | dissolved in the developing solution and only the pattern of the exposure site | part remained.

TABLE 2

Referring to Table 2, it was confirmed that the developing time of the photosensitive compositions prepared in Examples 4 to 6 did not take long compared to Comparative Example 2.

Color characteristic and contrast ratio evaluation

The color characteristics were spin-coated the compositions prepared from the examples and the comparative examples at 10 cm * 10 cm glass at each rotational speed (300, 500, 700) to perform a prebaking on a hot plate at 100 ℃ using an exposure machine After UV exposure at 60 mJ / cm and heat treatment at 230 ° C. for 30 minutes, color characteristics were measured using a spectrophotometer (MCPD3000).

In addition, the contrast ratio is measured by using a contrast ratio measuring instrument (Tsubosaka Co., Ltd.) between the two polarizing film, the value of measuring the ratio of the value when the light is perpendicular to the cross and parallel to the polarizing film to be.

[Table 3]

In addition, referring to Table 3, the color filter using the photosensitive resin composition prepared in Examples 4 to 6 was confirmed that the brightness and contrast ratio is significantly superior to Comparative Example 2.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (8)

(A) a dispersion resin which is an unsaturated ethylene oligomer represented by the following formula (1), a homopolymer thereof, or a copolymer of the unsaturated ethylene oligomer and an ethylenically unsaturated monomer, (B) carboxyl group-containing acrylic binder resin, (C) photopolymerizable monomer, (D) photoinitiator, (E) pigments and (F) Photosensitive resin composition for color filters containing a solvent. [Formula 1]

(In the formula 1, R ₁ and R ₁ ′ are the same or different from each other, and each independently, a C ₁ to C ₄ aliphatic hydrocarbon group, R ₂ and R ₂ ′ are the same or different from each other and are each independently a hydrogen atom or a methyl group, A ₁ is a copolymerization functional group including a repeating unit of Formula 2 and a repeating unit of Formula 3. [Formula 2]

(3)

(In Chemical Formulas 2 and 3, X ₁ and X ₁ ′ are the same or different from each other and are each independently residues of an aliphatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, or a combination thereof; Y ₁ and Y ₁ ′ are the same or different from each other and are each independently residues of a polyhydric alcohol, and at least one of Y ₁ and Y ₂ comprises an ionic group.) The method of claim 1, At least one of Y ₁ and Y ₁ ′ of Formulas 2 and 3 includes at least one structure of Formulas 4 to 6 below. [Formula 4]

[Chemical Formula 5]

[Formula 6]

(In Chemical Formulas 4 to 6, R ₃ and R ₃ ′ are the same or different from each other and are each independently an aliphatic hydrocarbon group, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, R ₅ , R ₆ and R ₇ are the same or different and are each independently a hydrogen atom, an aliphatic hydrocarbon group of C ₁ to C ₂₄ , or an aromatic hydrocarbon group of C ₆ to C ₂₀ , M is a monovalent metal.) The method of claim 2, The other one of the formula Y and Y 'is a photosensitive resin composition for color filters that are residues of glycols or alcohol amines. The method of claim 1, X ₁ and X ₁ ′ of Formula 1 are the same or different from each other and each independently a hexamethylene group, toluene group, diphenylmethylene group, 2,2,4-trimethylhexamethylene group, p-phenylene group, 4,4 The photosensitive resin composition for color filters chosen from the group which consists of a dicyclo hexamethylene group, m-xylene group, a naphthalene group, a cyclohexylene group, and an isopron group. The method of claim 1, (A) a dispersion resin which is an unsaturated ethylene oligomer represented by the following formula (1), a homopolymer thereof, or a copolymer of the unsaturated ethylene oligomer and an ethylenically unsaturated monomer, 0.5 to 5.0 wt% (B) Carboxyl group-containing acrylic binder resin, 0.5 to 30% by weight (C) photopolymerizable monomer, 0.5-30 weight% (D) photoinitiator, 0.1 to 10 weight% (E) pigment, 0.1 to 40% by weight; And (F) Photosensitive resin composition for color filters containing a solvent of remainder. The method of claim 1, Other ethylenically unsaturated monomers copolymerizable with the unsaturated ethylene oligomer of Formula 1 may include alkenyl aromatic monomers; Unsaturated carboxylic acid esters; The photosensitive resin composition for color filters chosen from the group which consists of unsaturated carboxylic acid amino alkyl esters, carboxylic acid vinyl esters, unsaturated carboxylic acid glycidyl esters, a vinyl cyanide compound, unsaturated amides, and a combination thereof. The method of claim 1, The dispersion resin photosensitive resin composition for a color filter having a weight average molecular weight of 10,000 to 70,000. The color filter manufactured using the photosensitive resin composition of any one of Claims 1-7.