KR20100098882A - Photosensitive resin composition for color filter and color filter using same - Google Patents

Abstract

PURPOSE: A photosensitive resin composition for a color filter is provided to obtain excellent heat resistance and chemical resistance and to be used for forming the color filter on a TFT array substrate to obtain a high aperture ratio and high contrast ratio. CONSTITUTION: A photosensitive resin composition for a color filter includes 5-50 weight% of an acrylic binder resin, 0.2-20 weight% of a photopolymerizable monomer, 0.1-10 weight% of a photopolymerization initiator, 0.1-40 weight% of a pigment, 1-60 weight% of a copolymer resin which is marked by chemical formula 1, and a solvent. In chemical formula 1, r is an integer of 1-5. The copolymer resin has an average molecular weight(Mw) of 1,000-100,000. The average molecular weight of the acrylic binder resin is 3,000-150,000.

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, excellent in heat resistance and chemical resistance, and useful for forming a color filter on a TFT array substrate for high opening ratio and high contrast ratio. It relates to a photosensitive resin composition for a color filter that can be used easily and a color filter using the same.

Color filters are used in liquid crystal displays (LCDs), optical filters of cameras, and the like, and are manufactured by applying a fine region colored in three or more colors onto a solid state imaging device or a transparent substrate. Such colored thin films are usually formed by dyeing, printing, electrodeposition, pigment dispersion, or the like.

In the dyeing method, an image having a dye-based substrate such as a natural photosensitive resin such as gelatin, an amine-modified polyvinyl alcohol, an amine-modified acrylic resin, etc. is formed on a substrate in advance and then dyed with a dye such as a direct dye to form a colored thin film. In order to form a multi-colored thin film on the same substrate, flameproof processing must be performed every time the color is changed, and thus, the process is very complicated and the time is delayed. In addition, although the clarity and dispersibility of the dyes and resins generally used are good, there are disadvantages in that light resistance, moisture resistance and heat resistance, which are the most important characteristics, are poor. For example, although an azo compound and an azide compound are used as the dye, there is a disadvantage in that heat resistance and durability are inferior to the pigment type.

In the printing method, after printing the ink which disperse | distributed the pigment to thermosetting or photocurable resin, a colored thin film is formed by hardening with heat or light. Although the printing method can reduce the material cost compared to other methods, there are disadvantages in that it is difficult to form highly precise and detailed images, and that the thin film layer is not uniform. Korean Unexamined Patent Publication No. 1995-7003746 proposes a method for manufacturing a color filter using an inkjet method, since the photosensitive resin composition for color filters sprayed from a nozzle by dye printing is precisely and precisely pigmented. Like the dyeing method, there is a disadvantage that the durability and heat resistance is poor.

In contrast, Korean Patent Publication Nos. 193-7000858 and Korean Patent Publication No. 1996-0029904 propose electrodeposition methods using an electroprecipitation method. Electrodeposition methods can form precise colored thin films and use pigments. Therefore, it has excellent heat resistance and light resistance, but if the pixel size and electrode pattern become finer in the future, color unevenness may appear due to electrical resistance at both ends or the thickness of the colored thin film becomes thick, so that the color filter requires high precision. There is a disadvantage that it is difficult to apply to the production.

On the other hand, the pigment dispersion method is a method for forming a colored thin film by repeating a series of processes of applying, exposing, developing and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. The pigment dispersion method can improve heat resistance and durability, which are the most important properties of the color filter, and have the advantage of keeping the thickness of the film uniform. For example, Korean Unexamined Patent Publication No. 1992-7002502, Korean Unexamined Patent Publication No. 195-7000359, Korean Patent Publication No. 194-0005617, and Korean Unexamined Patent Publication No. 1995-0011163 have a color filter using a pigment dispersion method. The manufacturing method of the photosensitive resin composition for water is proposed.

The colored photosensitive resin composition used for manufacturing the color filter by the pigment dispersion method generally consists of a binder resin, a photopolymerizable monomer, a photoinitiator, an epoxy resin, a solvent, other additives, etc. As the binder resin, for example, JP-A-7-140654 and JP-A-10-254133 use a carboxyl group-containing acrylic copolymer.

The manufacturing process of the color filter includes many chemical treatment steps. In order to maintain the pattern formed under such conditions, there is a need for a photosensitive resin for color filter that can improve the yield of the color filter with excellent chemical resistance while securing a development margin.

In particular, conventional color LCDs usually produce color filter substrates for displaying color images differently from the driving substrates on which TFTs are arranged, and fabricate the color filter substrates by bonding them with the driving substrates. However, in this method, the bonding precision was low, and the width of the light shielding layer had to be made large. For this reason, it was difficult to raise aperture ratio (ratio of opening which permeates light). In addition, in recent years, as the glass substrate and the LCD screen of the LCD are enlarged, the time for the liquid crystal composition to be disposed on the entire surface of the substrate during the vacuum injection of the liquid crystal is getting longer. For this reason, as a new technique, a manufacturing method for significantly shortening the bonding time by printing a seal material and dropping liquid crystals has been proposed. However, when such a method is adopted, there is a problem that the alignment accuracy is lowered.

On the other hand, a method of forming a color filter on a TFT array substrate for driving a TFT type color LCD has been proposed. As a result, the surface of the color filter substrate becomes unnecessary, and the surface is formed by simple sputtering. In this case, the two substrates may be bonded to each other to facilitate alignment and increase the aperture ratio.

However, when forming a color filter on a TFT array substrate, since a pixel electrode is formed on a color filter by the photolithographic method using the normal positive photosensitive resin composition, it is necessary to peel a photosensitive resin film after electrode formation. That is, a transparent electrode film is formed on the colored pixel of a color filter, positive type photosensitive resin composition is apply | coated on this transparent electrode film, and a pixel electrode is formed on it by patterning, exposure, and a development process. Since the photosensitive resin film which remain | survives on a pixel electrode is removed with a peeling liquid after forming a pixel electrode, the photosensitive resin composition needs tolerance to a peeling liquid. The conventional photosensitive resin composition for color filters has a problem that such peeling liquid resistance is weak.

Therefore, in the related art, a transparent film (pixel protective film) having a peeling liquid resistance was formed on the color filter and a pixel electrode was formed. Moreover, in the method which did not apply a pixel protective film, in order to reduce the influence which a peeling solution has on the color filter, the peeling solution was processed for a long time under low temperature conditions.

However, such a conventional method has a problem that the number of processes or time is increased to lower the yield rate or the production efficiency. In order to solve this problem, a color filter using a radiation-sensitive composition having an expansion ratio of 5% or less with respect to a peeling solution of a cured film forming a colored layer of a COA method has been proposed. Moreover, the color filter which used the polyfunctional alicyclic epoxy compound as a thermal-polymerization crosslinking agent, and used the benzophenone peroxide as a thermal-polymerization initiator, and improved the thermal-polymerization crosslinking effect was proposed. According to this, it is possible to cure at a low temperature and a short time, so that a color filter having excellent durability and good adhesion can be obtained. However, in recent years, since the demand for high quality large screens is increasing, the development of high-performance color filters with high aperture ratio is desired.

One embodiment of the present invention is to provide a photosensitive resin composition for color filters excellent in heat resistance and chemical resistance.

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

According to one embodiment of the invention, (A) acrylic binder resin; (B) acrylic photopolymerizable monomer; (C) photoinitiator; (D) pigments; (E) The photosensitive resin composition containing the copolymer resin represented by following General formula (1) and (F) solvent is provided.

[Formula 1]

(In Formula 1, r is an integer of 1 to 5.)

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

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

The photosensitive resin composition for color filters of the present invention is excellent in heat resistance and chemical resistance, and can be usefully used when forming a color filter on a TFT array substrate for high opening ratio and high contrast ratio.

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 20 carbon atoms, "aryl group" means an aryl group having 6 to 30 carbon atoms, and "arylalkyl group" means an aryl having 7 to 30 carbon atoms. An alkyl group means an "alkylene group", and means an alkylene group having 1 to 20 carbon atoms, and an "alkoxyene group" means an alkoxylene group having 1 to 20 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 a 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 Substituted by at least one substituent selected from the group consisting of a cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms and a heterocycloalkyl group having 2 to 30 carbon atoms substituted or unsubstituted 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 and P.

Photosensitive resin composition for color filters according to an embodiment of the present invention, (A) acrylic binder resin; (B) acrylic photopolymerizable monomer; (C) photoinitiator; (D) pigments; (E) Copolymer resin represented by following formula (1) and (F) solvent are included.

[Formula 1]

(In Formula 1, r is an integer of 1 to 5.)

In addition, it may further comprise other additives (G).

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

(A) Acrylic Binder Resin

The acrylic binder resin according to the present invention may include an ethylenic copolymer of an ethylenically unsaturated first monomer having one or more carboxyl groups and an ethylenically unsaturated second monomer copolymerizable therewith. Here, the ethylenically unsaturated first monomer having a carboxyl group is 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 20 to 30% by weight, based on the total weight of the monomers forming the copolymer. It may be included in the content.

Examples of the first monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like, and include one or more of them. However, it is not limited to this.

Examples of the second monomers include alkenyl aromatic compounds such as styrene, α-methyl styrene, vinyl toluene, 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 ester compounds 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 ester compounds such as 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate and 2-dimethyl amino ethyl methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amide compounds, such as acryl amide and methacryl amide, are mentioned, but it is not limited to this. The ethylenic copolymers used in the present invention comprise at least one second monomer of these.

Specific examples of the ethylenic copolymer composed of the above monomers include methacrylic acid / methyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene air Copolymers, methacrylic acid / benzyl methacrylate / 2-hydroxy ethyl methacrylate copolymers, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymers, and the like. It is not limited.

In addition, the photosensitive resin composition for a color filter according to the present invention, in order to achieve a fine pattern important in a color filter such as a COA method, and to secure excellent heat resistance and chemical resistance, the above-described formula 2 to 6 together with the ethylenic copolymer It may further include an acrylic copolymer containing a repeating unit represented.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

(In Chemical Formulas 2 to 6,

R ₁ is hydrogen or methyl,

R ₂ is hydrogen, a hydroxy group, a carboxyl group, a halogen, a haloalkyl group (wherein the alkyl group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and -CO-R ₇ -COOH, wherein R ₇ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted alkoxylene group having 1 to 10 carbon atoms, and

R ₃ is a carboxy group or -CONHR ₈ (wherein R ₈ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms), R ₄ is a carboxy group, R ₃ and R ₄ are fused to each other to form a ring,

R ₅ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

R ₆ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms,

l is an integer from 1 to 5,

When the molar ratios of Formulas 2 to 6 are expressed by m, n, o, p and q, respectively, 5≤m≤50, 1≤n≤20, 5≤o≤20, 10≤p≤100, and 10≤q≤ 100.)

The acrylic copolymer including a repeating unit represented by Formulas 2 to 6 containing an aliphatic hydrocarbon at the side chain (side branch chain) terminal has a structure similar to a photoreaction functional group included in the acrylic photopolymerizable monomer described below. Radicals induced by the photopolymerization initiator described in may be added to cause crosslinking by photopolymerization reaction in the resin.

The degree of crosslinking (crosslinking degree) by the acrylic copolymer may be determined according to the composition ratio of the acrylic photopolymerizable monomer and the photopolymerization initiator described below, and accordingly, control of the composition ratio of the acrylic photopolymerizable monomer and the photopolymerization initiator By the crosslinking degree can be adjusted.

The weight average molecular weight (Mw) of the acrylic binder resin may be within the range of 3,000 to 150,000, preferably 5,000 to 50,000. The acid value of the acrylic binder resin is preferably in the range of 20 to 150 mgKOH / g, more preferably 50 to 120 mgKOH / g. When the weight average molecular weight and the acid value of the acrylic binder resin are in the above range, excellent developability can be obtained.

It is preferable that the usage-amount of the said acrylic binder resin is 5 to 50 weight% with respect to the total amount of the photosensitive resin composition for all color filters. When the content of the acrylic binder resin is in the above range, the developability to the alkaline developer is excellent, the crosslinkability is good, the surface roughness is reduced, and the chemical resistance is good, and the pattern tearing does not occur.

In addition, when using an acrylic copolymer including a repeating unit represented by the formula (2) to 6, the content is preferably used in an amount of 10 to 70% by weight relative to the total amount of the acrylic binder resin. When the content of the acrylic copolymer including the repeating unit represented by Formulas 2 to 6 is in the above range, the chemical and chemical resistance improving effects are large, the stability of the pattern is good, and the light transmittance is not lowered.

(B) Acrylic Photopolymerizable Monomer

Examples of the acrylic photopolymerizable monomer used in the present invention include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacryl Latex, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A di Acrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4- Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. .

The amount of the acrylic photopolymerizable monomer is preferably 0.5 to 20% by weight based on the total amount of the photosensitive resin composition for color filters. When the content of the acrylic photopolymerizable monomer is in the above range, the corners of the pattern are formed cleanly, and developability in an alkaline developer is good.

(C) photopolymerization initiator

As an example of the photoinitiator used for this invention, a triazine type compound, an acetophenone type compound, a benzophenone type compound, a thioxanthone type compound, a benzoin type compound, an oxime type compound, etc. can be used.

Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimeth Methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 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- (trichloromethyl (4'-methoxy styryl) -6-triazine, and the like.

Examples of the acetophenone compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methyl propiophenone, pt-butyl trichloro acetophenone and pt- Butyl dichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propane-1- On, 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) -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'- Dichloro benzophenone, 3,3'-dimethyl-2-methoxy 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.

The benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl 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 the present invention, 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 used in 0.1 to 10% by weight based on the total amount of the photosensitive resin composition for color filters. When the content of the photopolymerization initiator is in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and does not cause a decrease in transmittance due to the unreacted initiator remaining after the photopolymerization.

(D) pigment

As the pigment, a pigment having a color such as red, green, blue, yellow, violet, or the like may be used. These are condensed polycyclic pigments, such as an anthraquinone pigment and a perylene pigment, a phthalocyanine pigment, an azo pigment, etc., Any one of these can be used individually, or can mix and use 2 or more types. It is preferable to use two or more kinds of mixtures for adjusting the maximum absorption wavelength and for adjusting the cross point and the cross talk.

The pigment may be prepared in a pigment dispersion dispersed in a solvent and included in the photosensitive resin composition for color filters.

In addition, a dispersant may be used as necessary to uniformly disperse the pigment component in the pigment dispersion. For this purpose, a nonionic, anionic or cationic dispersant may be used, for example, polyalkylene glycol and esters thereof. Polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like can be used. . These dispersants can be used individually by 1 type or in combination of 2 or more types as appropriate.

In addition, by using the first acrylic resin containing the above carboxyl group together with the dispersant, not only can the stability of the pigment dispersion be improved, but also the pattern of the pixel can be improved.

The primary particle diameter of the pigment may be 10 to 80 nm, preferably 10 to 70 nm. When the primary particle size falls within the particle size range, the pigment is excellent in stability in the pigment dispersion and there is no fear of lowering the resolution of the pixel.

It is preferable that the usage-amount of the said pigment is 0.1-40 weight% with respect to the total amount of the photosensitive resin composition for color filters. When the content of the pigment is in the above range, the coloring effect and developing performance are appropriate.

(E) copolymer resin of formula (1)

The photosensitive resin composition for color filters of the present invention may further include a copolymer resin represented by the following Chemical Formula 1.

[Formula 2]

(In Formula 2, r is an integer of 1 to 5.)

The molecular weight of the copolymer resin having the structure of Formula 1 is not particularly limited, but the number of repeating units is 5 to 20, or preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 20,000. . Sufficient sclerosis | hardenability can be obtained within the said range, and the molecular weight of the said copolymer resin is preferable because it is excellent in solvent solubility and applicability | paintability.

The copolymer resin may be included in 1 to 60% by weight, preferably 3 to 30% by weight based on the total amount of the photosensitive resin composition for color filters. The content of the copolymer resin is preferred because it is excellent in heat resistance, chemical resistance, and coating property by a repeating process.

(F) solvent

The solvents include ethylene glycol acetate, ethyl cellosolve, ethyl ethoxy propionate , ethyl lactate, polyethylene glycol, and the like, and the solvents include ethylene glycol compounds such as ethylene glycol and diethylene glycol; Glycol ether compounds such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; Glycol ether acetate compounds such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol; Propylene such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether Glycol ether compounds; Propylene glycol ether acetate compounds such as propylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; Amide compounds such as N-methyl pyrrolidone, dimethyl formamide, and dimethyl acetamide; Ketone compounds such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone; Petroleum compounds such as toluene, xylene, and solvent naphtha; Ester compounds, such as ethyl acetate, butyl acetate, and an ethyl lactate, etc. are mentioned. As the solvent of the present invention, any one of these species may be used alone, or two or more thereof may be mixed and used.

The amount of the solvent used is used in the amount of remainder, preferably in an amount of 20 to 90% by weight. 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 1 μm or more.

(G) other additives

The photosensitive resin composition for color filters of this invention may further contain the dispersing agent mentioned above so that a pigment (D) component may be disperse | distributed uniformly in a solvent (E) other than the component of said (A)-(F).

In addition, to prevent stains and spots during application, and to prevent the formation of residues due to leveling properties or undeveloped, malonic acid; 3-amino-1,2-propanediol; Silane coupling agents having a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; It may further include other additives such as radical polymerization initiators. The amount of these additives to be used can be easily adjusted according to the desired physical properties.

The photosensitive resin composition for color filters of the present invention is prepared by using a suitable method such as spin coating or slit coating on a glass substrate on which nothing is applied and a glass substrate on which SiNx (protective film) is applied to a thickness of 500 to 1500 kPa. To 3.4 μm in thickness. After application, light is irradiated to form a pattern required for the color filter. After irradiating the light, the coating layer is treated with an alkaline developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. 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.

In general, the negative photosensitive resin is not easily stripped in the organic solvent, so that the lower layer may be contaminated by the residue. In addition, as compared with the positive photosensitive resin, the adhesion to the lower layer is weak, and thus the undercut may be increased. The photosensitive resin composition for color filters of this invention is excellent in the resistance to the peeling liquid of such a negative photosensitive resin, prevents contamination of a lower film, and improves adhesiveness with a lower film.

Hereinafter, the present invention will be described in more detail with reference to preferred examples and comparative examples. However, the following examples are for illustrative purposes only and do not limit the invention.

Synthesis Example 1; Synthesis of acrylic copolymer including repeating units represented by Formulas 2 to 6]

In a flask equipped with a cooling tube and a stirrer, 10% by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) (initiator), 10% by weight of carboxy polyvalerolactone methacrylate (formula 2) %, Methacrylic acid (corresponding to Formula 3) 25 wt%, N-phenyl maleimide (corresponding to Formula 4) 5 wt%, styrene (corresponding to Formula 5) 5 wt%, benzyl meta 45 parts by weight of methacrylate (corresponding to Chemical Formula 6) and propylene glycol monomethyl ether acetate (PGMEA, solvent) were added to 200 parts by weight based on 100 parts by weight of the total amount of the initiator and the monomer, and then stirring was gradually started under a nitrogen atmosphere. It was. The reaction solution was heated to 80 ° C. and stirred for 8 hours to polymerize the second acrylic binder resin containing aliphatic hydrocarbon. Solid content concentration of the 2nd acrylic binder resin solution obtained by the above method was 30 weight%, and the weight average molecular weight was 31,000. In this case, the weight average molecular weight is a polystyrene converted average molecular weight measured using GPC (Gel Permeation Chromatography).

Preparation of the photosensitive resin composition for color filters

Example 1

Using the components shown in Table 1 below to prepare a photosensitive resin composition as follows. First, after dissolving the photopolymerization initiator in the solvent, it was stirred at room temperature for 2 hours. Then, an acrylic binder resin and an acrylic photopolymerizable monomer were added and stirred at room temperature for 2 hours. After the pigment dispersion was added thereto, the mixture was stirred at room temperature for 1 hour. Subsequently, a copolymerized resin of Formula 1 and a fluorine-based surfactant were added thereto, followed by stirring at room temperature for 1 hour to prepare a photosensitive resin composition for color filters according to the present invention. The solution was filtered three times to remove impurities.

TABLE 1

Furtherance Content [g] (A-1) Acrylic Binder Resin (Ethylene Copolymer) (a1) / (a2) = 25/75 (w / w), molecular weight (Mw) = 25,000, acid value = 95 mgKOH / g 6.0 (a1): methacrylic acid (a2): benzyl methacrylate (A-2) acrylic binder resin (acrylic copolymer) Copolymer prepared in Synthesis Example 1 3.9 Molecular weight (Mw) = 31,000, acid value = 110 mgKOH / g (B) Acrylic Photopolymerizable Monomer Dipentaerythritol hexaacrylate (DPHA) 4.1 (C) photopolymerization initiator IGACURE OXE02 from Ciba Specialty Chemicals 0.2 (D) Pigment Dispersion 46.8 BT-CF (Ciba Specialty Chemicals, Red Pigment) (6.2) 2RP-CF (Ciba Specialty Chemicals, Yellow Pigment) (2.8) BYK21208 (BYK, Dispersant) (2.4) Acrylic binder resin of the above (A-1) (5.4) PGMEA (solvent) (30.0) (E) copolymer resin of formula (1) SMA-20 (Sartomer) 3.5 (F) solvent PGMEA 24.0 Ethylethoxy propionate 11.4 (G) additive F-475 (DIC, fluorine-based surfactant) 0.1

[Example 2]

(E) A photosensitive resin composition for color filters was manufactured in the same manner as in Example 1, except that 1.5 g of SMA-20 (copolymer) was used instead of 3.5 g.

Example 3

A photosensitive resin composition for color filters was manufactured in the same manner as in Example 1 except that the acrylic binder resin (acrylic copolymer) of (A-2) was not used. 9.9 g of an acrylic binder resin (ethylenic copolymer) was used.)

Comparative Example 1

(E) A photosensitive resin composition for color filters was manufactured in the same manner as in Example 1 except that SMA-20 (copolymer) was not used. (In this case, acrylic binder resin (A-1) ( Ethylenic copolymer) was used at 9.5 g.)

Comparative Example 2

(E) A photosensitive resin composition for color filters was manufactured in the same manner as in Example 1, except that the same amount of epoxy acrylic carboxylate resin (EOCN, Nippon Kayaku Co., Ltd.) was used in place of SMA-20 (copolymer). It was.

Stripper resistance evaluation

Peeling liquid tolerance evaluation was performed using the photosensitive resin composition manufactured in the said Examples 1-3 and Comparative Examples 1-2.

Using a spin-coater (K-Spin8 from KDNS), a glass substrate coated with a transparent bare glass and silicon nitride (SiNx) coated with nothing at a thickness of 500 mm3 Above, the photosensitive resin composition of Examples 1-3 and Comparative Examples 1-2 was apply | coated in thickness of 3 micrometers. After soft-baking at 80 ° C. for 150 seconds using a hot-plate, and exposing at a power of 60 mJ using an exposure machine (I10C manufactured by Nikon), the developer The developing temperature was 25 ° C., a developing time of 60 seconds, a washing time of 60 seconds, and spin-drying for 25 seconds. At this time, a 1% by weight aqueous potassium hydroxide solution was used as the developer. Thereafter, the mixture was hard-baked for 30 minutes in an oven at 230 ° C., and then immersed in a 70 ° C. stripping solution (PRS-2000, JTBaker) for 10 minutes, followed by deionized water (DIW). warer) and dried.

The color change of the photosensitive resin composition coating film prepared by the above method was measured using a colorimeter (spectrophotometer, MCPD3000 of Otsuka Electronics Co., Ltd.), and the peeling state was observed using an optical microscope, and the results were classified as follows. It is shown in Table 2 below.

<Color change>

-If the color change after the stripping solution is weak: excellent

-If the color change after the stripping solution is underway: insufficient

-If the color change is strong after peeling liquid treatment: Poor

<Peel state>

-Without peeling of the photosensitive resin composition coating film: excellent

-If the photosensitive resin composition coating film is partially peeled off: insufficient

-When the photosensitive resin composition coating film peels mostly: bad

TABLE 2

division Color change Peeling state Bare glass SiNx Bare glass SiNx Example 1 Great Great Great Great Example 2 Great Great Great Great Example 3 Great Great Great Great Comparative Example 1 Bad Bad Bad Bad Comparative Example 2 Great Inadequate Inadequate Bad

Referring to Table 2, the photosensitive resin composition coating films of Examples 1 to 3 according to the present invention have little color change with respect to the stripping solution, but do not have peeling of the coating film. It can be confirmed that the resistance is excellent.

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 (9)

(A) acrylic binder resin; (B) acrylic photopolymerizable monomer; (C) photoinitiator; (D) pigments; (E) a copolymer resin represented by the following formula (1); And (F) solvent Photosensitive resin composition for color filters comprising a. [Formula 1]

(In the formula 1, r is an integer from 1 to 5. The method of claim 1, The photosensitive resin composition for color filters, (A) 5 to 50% by weight of the acrylic binder resin; (B) 0.5 to 20% by weight of the acrylic photopolymerizable monomer; (C) 0.1 to 10% by weight of the photopolymerization initiator; (D) 0.1 to 40% by weight of the pigment; (E) 1 to 60% by weight of the copolymer resin represented by Formula 1; And (F) the solvent balance Photosensitive resin composition for color filters comprising a. The method of claim 1, The weight average molecular weight (Mw) of the copolymer resin represented by the formula (1) is 1,000 to 100,000 of the photosensitive resin composition for color filters. The method of claim 1, The weight average molecular weight (Mw) of the acrylic binder resin is 3,000 to 150,000 photosensitive resin composition for color filters. The method of claim 1, The acid value of the acrylic binder resin is 20 to 150 mgKOH / g photosensitive resin composition for color filters. The method of claim 1, The acrylic binder resin further comprises an acrylic copolymer comprising a repeating unit represented by the following formulas (2) to (6). [Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

(In Chemical Formulas 1 to 5, R ₁ is hydrogen or methyl, R ₂ is hydrogen, a hydroxy group, a carboxyl group, a halogen, a haloalkyl group (wherein the alkyl group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and -CO-R ₇ -COOH, wherein R ₇ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted alkoxylene group having 1 to 10 carbon atoms, and R ₃ is a carboxy group or -CONHR ₈ (wherein R ₈ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms), R ₄ is a carboxy group, R ₃ and R ₄ are fused to each other to form a ring, R ₅ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, R ₆ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, l is an integer from 1 to 5, When the molar ratios of Formulas 2 to 6 are expressed by m, n, o, p and q, respectively, 5≤m≤50, 1≤n≤20, 5≤o≤20, 10≤p≤100, and 10≤q≤ 100.) The method of claim 6, The acrylic copolymer including the repeating unit represented by Formulas 2 to 6 may be used based on the total amount of the acrylic binder resin. It is contained in 10 to 70% by weight photosensitive resin composition for color filters. The method of claim 1, The photosensitive resin composition is a dispersant; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents having a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; A photosensitive resin composition for color filters, further comprising an additive selected from the group consisting of a radical polymerization initiator and mixtures thereof. The color filter manufactured using the photosensitive resin composition for color filters of any one of Claims 1-8.