KR101661672B1 - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

(상기 화학식 1에서 각 치환기의 정의는 명세서에서 기재된 바와 같다.)(A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a pigment dispersion; (E) a dispersion resin comprising a copolymer represented by the following formula (1); And (F) a solvent, and a color filter using the same.
[Chemical Formula 1]

(The definition of each substituent in the above formula (1) is as described in the specification.)

Description

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

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

Recently, as the spread of the large-screen liquid crystal display device has expanded, a demand for a new performance enhancement for the liquid crystal display device has been increasing. Among the components of the liquid crystal display device, the color filter is the most important color realizing device. Research is continuing.

The color filter is made of dyes or pigments of red (R), green (G), and blue (B), and this dye material serves to convert the white light of the backlight unit into respective corresponding colors. It must have excellent heat resistance, chemical resistance, and pattern processability that do not fade or discolor under exposed ultraviolet, acid, or base conditions.

The color filter using the photosensitive resin composition can be produced by coating three or more kinds of hues on a transparent substrate mainly by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method and the like. Recently, a pigment dispersion method is widely used.

On the other hand, in the case of a photosensitive resin composition, an excessive amount of pigment is often used in order to realize a high color reproducibility. In this case, the pattern is not formed well or the developing time is remarkably slowed. In order to solve this problem, there has been an attempt to add a developing monomer to the photosensitive resin composition. However, in this case, the developing property is slightly improved, the development time is slow, the adhesion and chemical resistance of the formed pattern are greatly reduced, There is a problem that pattern subtraction occurs due to the pattern.

Therefore, research on methods for improving not only the color characteristics but also the chemical properties, such as the chemical properties, by using the pigment dispersion method has been continued.

One embodiment is to provide a photosensitive resin composition excellent in color characteristics and processability.

Another embodiment is to provide a method for producing a pigment dispersion used for producing the photosensitive resin composition.

Another embodiment is to provide a pigment dispersion prepared using the above-described method for producing a pigment dispersion.

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

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

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁷ to R ¹⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ¹ to L ⁴ each independently represent a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.

For example, R ⁷ to R ¹⁴ each independently may be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and each of L ¹ to L ⁴ is independently a single bond or a substituted or unsubstituted C1 to C20 alkyl It can be a ring.

The dispersion resin may have a weight average molecular weight of 8,000 g / mol to 15,000 g / mol.

The pigment dispersion may comprise a pigment.

The pigment may be contained in an amount of 10 to 30% by weight based on 100% by weight of the pigment dispersion.

The pigment may comprise a green pigment, a red pigment or a combination thereof.

The binder resin may be an acrylic binder resin.

The photosensitive resin composition comprises 1 to 30% by weight of the binder resin; 0.1% to 20% by weight of the photopolymerizable monomer; 0.01 to 10% by weight of the photopolymerization initiator; 10% to 70% by weight of the pigment dispersion; 0.1% by weight to 35% by weight of the dispersion resin; And solvent balance.

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; A radical polymerization initiator; Or a combination thereof.

Another embodiment is a process for preparing a solvent, comprising: preparing a solvent; Introducing a dispersion resin containing the copolymer represented by the formula (1) into the solvent; Introducing a dispersant into the solvent; Introducing a pigment into the solvent; And a step of stirring the dispersion resin, the dispersing agent and the solvent into which the pigment is added.

Another embodiment provides a pigment dispersion prepared using the method of making the pigment dispersion.

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

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

Since the photosensitive resin composition is excellent in processability such as color characteristics and chemical resistance, it can be usefully used for a color filter.

1 is an optical microscope photograph of a color filter pattern according to Example 1. Fig.
2 is an optical microscope photograph of a color filter pattern according to Comparative Example 1. Fig.
3 is a photograph of the pattern profile of the color filter according to the fourth embodiment.
4 is a photograph of the pattern profile of the color filter according to Comparative Example 4. Fig.

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

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, An ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C30 heteroaryl groups, or combinations thereof.

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

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

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment comprises (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a pigment dispersion; (E) a dispersion resin comprising a copolymer represented by the following formula (1); And (F) a solvent.

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁷ to R ¹⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ¹ to L ⁴ each independently represent a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.

For example, R ⁷ , R ⁸ and R ¹¹ to R ¹⁴ may each independently be a hydrogen atom, a hydroxyl group or a substituted or unsubstituted C 1 to C 20 alkyl group, and R ⁹ and R ¹⁰ are each independently a hydrogen atom or a substituted Or an unsubstituted C1 to C20 alkyl group, and each of L ¹ to L ⁴ may independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

In general, the photosensitive resin composition prepared by using the pigment dispersion method has been generally modified to improve the binder resin or the pigment itself in order to improve the color characteristics, heat resistance, chemical resistance, and the like.

However, the photosensitive resin composition according to one embodiment can improve the color characteristics and the processability by introducing and improving the dispersing resin for dispersing the pigment, rather than the binder resin or the pigment itself. That is, the photosensitive resin composition contains a dispersion resin, and the dispersed resin contains the copolymer represented by the above formula (1), so that the development speed, the chemical resistance, the pattern forming property And the like can be improved.

Specifically, the dispersion resin includes a copolymer represented by Chemical Formula 1 at the time of film formation, so that it is possible to improve the color characteristic such as luminance by excellent transparency. Also, as the content of monomers for improving the developing property in the monomer composition in the copolymer is increased, the developing property is excellent and the pattern processability can be improved.

Each component will be described in detail below.

(E) Dispersion resin

The photosensitive resin composition according to one embodiment includes a dispersion resin that allows the pigment component to be uniformly dispersed in a pigment dispersion to be described later. The dispersion resin may be contained in a pigment dispersion described later.

The dispersion resin includes the copolymer represented by the formula (1).

The dispersion resin represented by Formula 1 may have a weight average molecular weight of 8,000 g / mol to 15,000 g / mol, for example, 9,000 g / mol to 15,000 g / mol. When the dispersion resin has a weight average molecular weight within the above range, it is advantageous in improving the developability and securing the chemical resistance.

The dispersion resin may be contained in an amount of 1 wt% to 50 wt%, for example, 3 wt% to 40 wt% based on 100 wt% of the pigment dispersion. For example, the dispersion resin may be contained in an amount of 0.1% by weight to 35% by weight, for example, 0.3% by weight to 28% by weight based on 100% by weight of the photosensitive resin composition. When the dispersion resin is contained within the above range, effective dispersion can be achieved and dispersion stability can be ensured.

(D) Pigment dispersion

The photosensitive resin composition according to one embodiment includes a pigment dispersion.

Pigment dispersions generally include pigments and solvents, but have limitations in uniformly dispersing pigments. However, the pigment dispersion of one embodiment further includes the above-mentioned dispersion resin in addition to the pigment and the solvent to help uniform dispersion of the pigment. The pigment dispersion may be prepared by simply mixing the dispersion resin, the pigment, the solvent, and the like.

As the pigment, a red pigment, a yellow pigment, a blue pigment, a green pigment, a violet pigment, or a combination thereof may be used. These include condensed polycyclic pigments such as anthraquinone pigments and perylene pigments, phthalocyanine pigments, and azo pigments. Any one of these pigments may be used alone, or two or more pigments may be used in combination. It is preferable to use two or more kinds of them for adjustment of the maximum absorption wavelength and adjustment of cross point, cross talk and the like.

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

The yellow pigments have a C.I. Pigment yellow 139, C.I. Pigment yellow 138, C.I. Pigment yellow 150, etc. These may be used alone or in combination of two or more.

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

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

The primary particle diameter of the pigment may be from 10 nm to 80 nm, for example from 10 nm to 70 nm. When the primary particle diameter is within the above-mentioned particle diameter range, the stability in the pigment dispersion is excellent and there is no fear of deterioration of the resolution of the pixel, which is preferable.

The pigment may be contained in an amount of 10 to 30% by weight based on 100% by weight of the pigment dispersion. When the pigment content in the pigment dispersion is within the above range, color characteristics such as luminance can be improved.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether or 3-methoxy-1-butanol can be used. Among them, propylene glycol methyl ether acetate can be preferably used. At this time, it is preferable that the content of the solvent is adjusted so that the solid content of the pigment dispersion is 5 wt% to 30 wt%.

The solvent may be contained in an amount of from about 30% by weight to about 80% by weight based on 100% by weight of the pigment dispersion.

In addition, the pigment dispersion may further include a dispersant. As the dispersing agent, nonionic, anionic or cationic dispersing agents can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts , A sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine. These dispersants may be used singly or in combination of two or more.

The dispersing agent may be contained in an amount of 0.01 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, so that excellent stability, developability and patternability can be obtained.

In addition, the pigment dispersion further includes an acrylic resin containing a carboxyl group in addition to the above-mentioned dispersion resin, thereby improving the stability of the pigment dispersion and further improving the patterning of the pixels.

The amount of the pigment dispersion, for example, the pigment dispersion containing the dispersion resin is preferably 10% by weight to 70% by weight based on the total weight of the photosensitive resin composition. When the content of the pigment dispersion containing the dispersing resin is within the above range, reliability and developability such as color characteristics such as luminance and chemical resistance can be improved.

(A) Binder resin

The binder resin may be an acrylic binder resin.

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 to 50% by weight, for example, 10 to 40% by weight based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin include (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2- Acrylate copolymer, a (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but not limited thereto, and they may be used alone or in combination have.

The weight average molecular weight of the binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 15,000 g / mol. 　　 When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion with a substrate in the production of a color filter.

The binder resin may have an acid value of 20 mgKOH / g to 200 mgKOH / g, such as 80 mgKOH / g to 130 mgKOH / g. When the binder resin having the acid value is used, the resolution of the pixel pattern is excellent.

The binder resin may be used in an amount of 1 to 30% by weight based on the total amount of the photosensitive resin composition, 1% by weight to 20% by weight. When the binder resin is contained within the above range, the sensitivity and developability are excellent, the chemical resistance is improved, and the pattern peeling does not occur.

(B) Photopolymerization  Monomer

The photopolymerizable monomer may be an acrylic photopolymerizable monomer.

The acrylic photopolymerizable monomer may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl Terminus (meth) acrylate, trimethylolpropane may be a tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.

G the product as marketed, the photo-polymerizable monomer Examples, doah Gosei Kagaku Kogyo (Note)社of Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®, the same M-210 ^®, copper M- 240 ^® , M-6200 ^® , M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® and M-8060 ^® Etc; KAYARAD TC-110S ^® , TC-120S ^® , KAYARAD HDDA ^® , Copper HX-220 ^® , Copper R-604 ^® , Copper KAYARAD TMPTA ^® , Copper DPCA-20 ^® , Copper- 30 ^{®, ®} -60 copper, copper ^® -120 and the like; Osaka yukki Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®, V-260 ®, V-312 ®, V-335 HP ®, V-295 ®, East -300 ^®, East -360 ^® , there may be mentioned copper -GPT ^{®, ®} -3PA copper, copper ^® -400 and the like. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties. That is, the photopolymerizable monomer may be a photopolymerizable monomer not treated with an acid anhydride, a photopolymerizable monomer treated with an acid anhydride, or a combination thereof.

As described above, the photopolymerizable monomer can be crosslinked by photopolymerization reaction with each monomer in the dispersion resin.

The amount of the photopolymerizable monomer to be used may be 0.1 wt% to 20 wt%, for example, 1 wt% to 15 wt% with respect to the total amount of the photosensitive resin composition. When the content of the photopolymerizable monomer is within the above range, edges of the pattern are formed cleanly, and the pattern is formed with sufficient curing during exposure in the pattern forming step, and the reliability is excellent and developability to an alkaline developer is good.

(C) Light curing Initiator

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

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) Acetate and the like.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be included in an amount of 0.01 wt% to 10 wt%, for example, 0.5 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(F) Solvent

The solvent may be a pigment dispersion containing the dispersion resin, the binder resin, the photopolymerizable monomer, and a material having compatibility with the photopolymerization initiator but not reacting with the photopolymerizable monomer.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

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

The solvent may be included as a residual amount relative to the total amount of the photosensitive resin composition, specifically 20 wt% to 90 wt%. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coating property and excellent flatness can be maintained in a film having a thickness of 1 占 퐉 or more.

(F) Other additives

In order to prevent spots or spots during coating and to improve the leveling performance and to prevent the formation of residues due to unexposed phenomenon, the photosensitive resin composition is preferably prepared by adding malonic acid, 3-amino-1,2-propanediol, Or other additives such as a silane-based coupling agent containing a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

As the surfactant, a fluorochemical surfactant may be used. Examples of the fluorine-based surfactant, BM Chemie Corporation ^{BM-1000 ®, BM-1100} ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to desired properties.

The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be contained in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained in the above range, it has excellent adhesion, heat resistance and chemical resistance.

Another embodiment provides a method of making the pigment dispersion described above.

The method for preparing a pigment dispersion comprises: preparing a solvent; Introducing a dispersion resin containing the copolymer represented by the formula (1) into the solvent; Introducing a dispersant into the solvent; Introducing a pigment into the solvent; And stirring the solvent into which the dispersion resin and the pigment are introduced.

The copolymer represented by the formula (1), the dispersion resin, the pigment and the like are as described above.

Another embodiment provides a pigment dispersion prepared using the above-described method for producing a pigment dispersion.

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

A method of manufacturing the color filter is as follows.

The above-mentioned photosensitive resin composition is coated on the glass substrate by a suitable method such as spin coating, roller coating, spray coating or the like to a thickness of 0.5 占 퐉 to 10 占 퐉, for example, to form a resin composition layer.

Then, light is irradiated to form a pattern necessary for the color filter on the substrate on which the resin composition layer is formed. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV of 190 nm to 450 nm, specifically 200 nm to 400 nm can be irradiated. A photoresist mask may be further used in the above irradiation step. After the step of irradiating in this manner, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the non-exposed portions in the resin composition layer are dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, crack resistance and solvent resistance can be improved.

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

(Preparation of Pigment Dispersion)

Manufacturing example  One

(5 g, weight average molecular weight = 9000 g / mol), a pigment dispersant (BYK, 2.5 g), and G58 green (2 g) were added to a solvent (propylene glycol monomethyl ether acetate 14 g of the pigment was added, and the mixture was stirred at 40 캜 for 48 hours to prepare a pigment dispersion A.

(2)

Manufacturing example  2

A pigment dispersion B was prepared in the same manner as in Production Example 1, except that Y138 yellow pigment (BASF, 14 g) was used instead of G58 green pigment in Production Example 1.

Manufacturing example  3

The same procedure as in Production Example 1 was carried out except that a dispersion resin (trade name: NPR1520) was used instead of the dispersion resin (5 g, weight average molecular weight = 9000 g / mol) containing the copolymer represented by the formula To prepare a pigment dispersion C.

Manufacturing example  4

The same procedure as in Production Example 2 was carried out except that a dispersion resin (trade name: NPR1520) was used instead of the dispersion resin (5 g, weight average molecular weight = 9000 g / mol) containing the copolymer represented by the formula The pigment dispersion D was prepared.

Manufacturing example  5

A pigment dispersion E was prepared in the same manner as in Production Example 1 except that 14 g of R177 red pigment was used instead of G58 green pigment in Production Example 1. [

Manufacturing example  6

A pigment dispersion F was prepared in the same manner as in Production Example 1, except that 14 g of R254 red pigment was used instead of G58 green pigment in Production Example 1.

Manufacturing example  7

In the same manner as in Production Example 1 except that a dispersing resin (trade name: NPR1520) was used in place of the dispersion resin (5 g, weight average molecular weight = 9000 g / mol) containing the copolymer represented by Formula 2, (Yellow or orange or other pigment) (BASF, 14g) was used instead of the pigment (G).

Manufacturing example  8

The same procedure as in Production Example 6 was carried out except that a dispersing resin (trade name: NPR1520) was used instead of the dispersion resin (5 g, weight average molecular weight = 9000 g / mol) containing the copolymer represented by the formula The pigment dispersion H was prepared.

(Preparation of photosensitive resin composition)

Example  1 to Example  6 and Comparative Example  1 to Comparative Example  6

After the content of the photopolymerization initiator was precisely measured, the solvent was added and sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was completely dissolved. The binder resin and the photopolymerizable monomer were sequentially added thereto, followed by stirring for about 1 hour. Thereafter, the pigment dispersion and other additives were added, and finally the entire composition was stirred for 2 hours or more to prepare a photosensitive resin composition.

The composition of each component used in the production of the photosensitive resin composition is shown in Tables 1 and 2 below.

(Unit: wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Binder resin A 4.13 - 4.13 4.13 - - B - 4.13 - - 4.13 4.13 Photopolymerization  Monomer A 2.43 2.43 2.00 1.92 2.43 1.92 B 0.49 0.49 0.92 1.00 0.49 1.00 Light curing Initiator A 0.73 0.73 0.73 0.73 0.73 0.73 B 0.31 0.31 0.31 0.31 0.31 0.31 Pigment dispersion A 33.13 (13.8%) 33.13 (13.8%) 33.13 (13.8%) - - - B 27.37 (13.8%) 27.37 (13.8%) 27.37 (13.8%) - - - C - - - 33.13 (13.8%) 33.13 (13.8%) 33.13 (13.8%) D - - - 27.37 (13.8%) 27.37 (13.8%) 27.37 (13.8%) menstruum 31.05 31.05 31.05 31.05 31.05 31.05 additive A 0.20 0.20 0.20 0.20 0.20 0.20 B 0.16 0.16 0.16 0.16 0.16 0.16 Total 100.00 100.00 100.00 100.00 100.00 100.0

(In Table 1, the numbers in the parentheses indicate the content (% by weight) of the pigment with respect to each pigment dispersion (100% by weight)

(Unit: wt%) Example 4 Example 5 Example 6 Comparative Example 4 Comparative Example 5 Comparative Example 6 Binder resin A 4.13 - 4.13 4.13 - - B - 4.13 - - 4.13 4.13 Photopolymerization  Monomer A 2.43 2.43 2.00 1.92 2.43 1.92 B 0.49 0.49 0.92 1.00 0.49 1.00 Light curing Initiator A 0.73 0.73 0.73 0.73 0.73 0.73 B 0.31 0.31 0.31 0.31 0.31 0.31 Pigment dispersion E 33.13 (13.8%) 33.13 (13.8%) 33.13 (13.8%) - - F 27.37 (13.8%) 27.37 (13.8%) 27.37 (13.8%) - - G - - - 33.13 (13.8%) 33.13 (13.8%) 33.13 (13.8%) H - - - 27.37 (13.8%) 27.37 (13.8%) 27.37 (13.8%) menstruum 31.05 31.05 31.05 31.05 31.05 31.05 additive A 0.20 0.20 0.20 0.20 0.20 0.20 B 0.16 0.16 0.16 0.16 0.16 0.16 Total 100.00 100.00 100.00 100.00 100.00 100.0

(In Table 2, the numbers in the parentheses indicate the content (% by weight) of the pigment with respect to each pigment dispersion (100% by weight)

The types of the respective components shown in Table 1 and Table 2 are as follows.

Binder resin

 Binder resin A: Acrylic binder resin (available from MIYON Co., Ltd., NPR1520)

 Binder resin B: Acrylic binder resin (SMS, 300T)

Photopolymerization  Monomer

 Photopolymerizable monomer A: A photopolymerizable monomer (satomer, diphenyl pentaerythritol hexaacrylate)

 Photopolymerizable monomer B: Photopolymerizable monomer (SHIN-NAKAMURA CHEMICAL, A-BPE-20)

Light curing Initiator

 Photopolymerization initiator A: Oxime initiator 1 (TAKOMA, TPM-P07)

Photopolymerization initiator B: Oxime initiator 2 (CIBA, CGI-124)

Pigment dispersion

 Pigment dispersion A: The pigment dispersion prepared in Preparation Example 1

 Pigment dispersion B: The pigment dispersion prepared in Production Example 2

 Pigment dispersion C: The pigment dispersion prepared in Preparation Example 3

 Pigment dispersion D: The pigment dispersion prepared in Production Example 4

 Pigment dispersion E: The pigment dispersion prepared in Preparation Example 5

 Pigment dispersion F: The pigment dispersion prepared in Preparation Example 6

 Pigment dispersion G: The pigment dispersion prepared in Preparation Example 7

 Pigment dispersion H: Pigment dispersion prepared in Production Example 8

menstruum

 Propylene glycol monomethyl ether acetate (PGMEA)

additive

 Additive A: Surfactant (F559, DIC)

Additive B: Coupling agent (S-510, CHISSO)

Rating 1: Color characteristics  evaluation

Each of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was coated on a glass substrate having a thickness of 1 mm and degreased and cleaned at a thickness of 1 탆 to 2 탆 and heated at 90 캜 on a hot plate And dried for 3 minutes to obtain a coating film. The obtained coating film was cooled, irradiated with light at an exposure dose of 50 mJ / cm ² (based on 365 nm), and then dried in a hot air circulating drying oven at 230 ° C for 30 minutes. The color was measured through a spectrophotometer (MCPD3000 of Otsuka Electronics Co., Ltd.), and the results are shown in Table 3 below.

Color coordinates (Gx) Color coordinates (Gy) Luminance (Y) Example 1 0.261 0.625 52.1 Example 2 0.260 0.625 52.1 Example 3 0.262 0.625 52.2 Example 4 0.671 0.326 17.1 Example 5 0.673 0.327 17.4 Example 6 0.672 0.326 17.2 Comparative Example 1 0.260 0.625 52.1 Comparative Example 2 0.260 0.625 52.1 Comparative Example 3 0.259 0.625 52.1 Comparative Example 4 0.657 0.326 18.2 Comparative Example 5 0.671 0.327 17.3 Comparative Example 6 0.671 0.326 17.1

Evaluation 2: Chemical resistance evaluation

Each of the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 6 was coated on a glass substrate having a thickness of 1 mm by degreasing using a spin coater (K-Spin 8, KDNS) to a thickness of 2 탆 , And dried on a hot plate at 90 DEG C for 3 minutes to obtain a coating film. The obtained coating film was cooled, irradiated with light at an exposure dose of 100 mJ / cm ² (based on 365 nm), stored in a hot-air circulation drying furnace at 230 ° C for 30 minutes, and then evaluated. After immersing the specimen in a NMP solvent for 30 minutes, the color change was measured using a spectrophotometer (MCPD3000 manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 4 below.

<Evaluation criteria for chemical resistance>

&Amp; cir &amp;: When there is no change in color or when the color difference (DELTA E)

∘: When the color difference (ΔE) during the chemical solvent treatment is more than 1.0 and less than 3.0

DELTA: color difference (DELTA E) when the chemical solvent is treated is more than 3.0 and less than 5.0

Ⅹ: When the change of color is visually recognized or when the color difference (ΔE) is over 5.0

Evaluation 3: Evaluation of pattern profile

Each of the photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 6 was coated on a glass substrate having a thickness of 1 mm with a thickness of 3.0 탆 by using a spin coater (K-Spin 8, KDNS) And then dried on a hot plate at 80 DEG C for 150 seconds to obtain a coating film. Subsequently, a photomask was placed on each coating film and exposed using a high-pressure mercury lamp having a wavelength of 365 nm with varying exposure dose. Subsequently, the development BP was measured at a time (s) at which the pattern appeared at 30 DEG C under atmospheric pressure using a 1.33 wt% potassium hydroxide (KOH) aqueous solution, developed at 1.5 times (s) of the development BP, Respectively. Then, a post-baking process was performed in a hot air circulating drying oven at 230 DEG C for 25 minutes to prepare a pattern. The pattern thus prepared was subjected to optical zooming through an optical microscope at 500x magnification to measure an image, and the results are shown in Table 4 and Figs.

<Evaluation Criteria of Pattern Profile>

○: The shape of the pattern is well implemented without abnormality, and the pattern profile angle is 70 ° or less

Δ: The shape of the pattern was well implemented without abnormality, but when the pattern profile angle was 70 ° or more and less than 90 °

Ⅹ: If the shape of the pattern is abnormal and the pattern profile angle is 90 ° or more,

Development time (s) Chemical resistance Pattern profile Example 1 40 ◎ ○ Example 2 35 ◎ ○ Example 3 38 ◎ ○ Example 4 39 ◎ ○ Example 5 35 ◎ ○ Example 6 37 ◎ ○ Comparative Example 1 110 ◎ × Comparative Example 2 > 120 ○ × Comparative Example 3 98 × × Comparative Example 4 103 ◎ × Comparative Example 5 > 110 ○ × Comparative Example 6 95 × ×

Through the above Tables 3, 4, and 1 to 4, it can be seen that the color filters of Examples 1 to 6 are superior in color characteristics to those of Comparative Examples 1 to 6, It can be seen that the BP is short and the developability is excellent.

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

Claims (15)

(A) a binder resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a pigment dispersion;
(E) a dispersion resin comprising a copolymer represented by the following formula (1); And
(F) Solvent
: &Lt; EMI ID =
[Chemical Formula 1]

(In the formula 1,
R ¹ to R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁷ to R ¹⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.
The method according to claim 1,
In Formula 1,
R ⁷ to R ¹⁴ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
The method according to claim 1,
Wherein the dispersed resin has a weight average molecular weight of 8,000 g / mol to 15,000 g / mol.
The method according to claim 1,
Wherein the pigment dispersion comprises a pigment,
Wherein the pigment is contained in an amount of 10 to 30% by weight based on 100% by weight of the pigment dispersion.
5. The method of claim 4,
Wherein the pigment comprises a green pigment, a red pigment or a combination thereof.
The method according to claim 1,
Wherein the binder resin is an acrylic binder resin.
The method according to claim 1,
The photosensitive resin composition
1 to 30% by weight of the binder resin;
0.1% to 20% by weight of the photopolymerizable monomer;
0.01 to 10% by weight of the photopolymerization initiator;
10% to 70% by weight of the pigment dispersion;
0.1% by weight to 35% by weight of the dispersion resin; And
The solvent balance
.
The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; A radical polymerization initiator; Or a combination thereof. &Lt; / RTI &gt;
Preparing a solvent;
Introducing a dispersion resin containing a copolymer represented by the following formula (1) into the solvent;
Introducing a dispersant into the solvent;
Introducing a pigment into the solvent; And
Stirring the solvent into which the dispersion resin, the dispersing agent and the pigment are mixed,
&Lt; / RTI &gt;
[Chemical Formula 1]

(In the formula 1,
R ¹ to R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁷ to R ¹⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.
10. The method of claim 9,
In Formula 1,
R ⁷ to R ¹⁴ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
10. The method of claim 9,
Wherein the dispersion resin has a weight average molecular weight of 8,000 g / mol to 15,000 g / mol.
10. The method of claim 9,
Wherein the pigment is contained in an amount of 10% by weight to 30% by weight based on 100% by weight of the pigment dispersion.
10. The method of claim 9,
Wherein the pigment comprises a green pigment, a red pigment or a combination thereof.
14. A pigment dispersion produced by the method of any one of claims 9 to 13.
A color filter produced by using the photosensitive resin composition of any one of claims 1 to 8.

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