KR20130060037A - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) a copolymer comprising a structural unit represented by the following formula (1), (B) a carboxyl group-containing acrylic copolymer, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, (E) a dye and And a color filter using the same.
[Formula 1]

(Wherein each substituent is as defined in the specification).

Description

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

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

A color filter is used for a liquid crystal display (LCD), an optical filter of a camera, and the like, and is manufactured by coating a fine area colored with three or more colors onto a solid-state image sensor or a transparent substrate. Such a colored thin film is formed by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like.

The pigment dispersion method is mainly used because it can improve the heat resistance and durability, which are the most important properties of a color filter, and can keep the thickness of the film uniform.

The pigment dispersion method is a method in which a colored thin film is formed by repeating a series of steps of applying, exposing, developing, and thermally curing a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix.

The colored photosensitive resin composition used in the production of a color filter according to the pigment dispersion method generally comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent and other additives. As the binder resin, for example, in JP-A-7-140654 and JP-A-10-254133, a carboxyl group-containing acrylic copolymer is used.

However, there is a demand for a method capable of preventing reduction of contrast ratio and luminance caused by the particle size of pigments for the recent manufacture of LCDs having high brightness and contrast ratio. In such a method, there is a method of enhancing the dispersion of the pigment to reduce the size of the pigment particles, but there are technical limitations.

Accordingly, instead of increasing the degree of dispersion of the pigment, a method of replacing the pigment with a dye or adding a dye to a pigment dispersion has been developed.

On the other hand, the manufacturing process of the color filter includes many chemical processing steps. In order to maintain the pattern formed under such conditions, a photosensitive resin for a color filter capable of improving the yield of a color filter with excellent chemical resistance while maintaining a developing margin is required.

In the case of forming a color filter on a TFT array substrate for driving a TFT type color LCD, a pixel electrode is formed on the color filter by a photolithography method using a normal positive photosensitive resin composition, so that the photosensitive resin film is peeled There is a need. Therefore, the photosensitive resin composition is required to be resistant to peeling liquid.

In recent years, there has been an increasing demand for a high-quality large-sized screen. Therefore, it is desired to develop a high-performance color filter having a high aperture ratio.

An embodiment of the present invention is to provide a photosensitive resin composition which is excellent in heat resistance and chemical resistance, and can exhibit a high numerical aperture and a high contrast ratio.

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

One embodiment of the present invention is a copolymer comprising: (A) a copolymer comprising a structural unit represented by the following formula (1); (B) carboxyl group-containing acrylic copolymer; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E) a dye; And (F) a solvent.

[Formula 1]

(In the formula 1,

R ¹ , R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

R ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.)

The structural unit represented by the formula (1) may be contained in an amount of 0.05 to 50 mol% based on the total amount of the copolymer (A) containing the structural unit represented by the formula (1).

The copolymer (A) comprising the structural unit represented by the formula (1) may further include at least one of the structural units represented by the following formulas (2) to (6).

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

(In the above formulas 2 to 6,

R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ are each independently a hydrogen atom or a C 1 to C 20 alkyl group,

R ⁸ is a hydrogen atom, a halogen atom or a hydroxy group,

R ¹⁰ is a carboxyl group or CONHR (where, R is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group unsubstituted), and a, R ¹² is a carboxyl group, R ¹⁰ and R ¹² are fused together Ring,

R ¹⁴ is a substituted or unsubstituted C6 to C30 aryl group,

R ¹⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 cycloalkyl group,

m is an integer from 1 to 5.)

At least one of the structural units represented by the general formulas (2) to (6) may be contained in an amount of 1 to 50 mol% based on the total amount of the copolymer (A) containing the structural unit represented by the general formula (1).

The weight average molecular weight of the copolymer (A) containing the structural unit represented by the formula (1) may be 1,000 to 100,000 g / mol.

The amine value of the copolymer (A) containing the structural unit represented by the formula (1) may be 10 to 200 mg HCl / g.

The carboxyl group-containing acrylic copolymer (B) may include a structural unit represented by the following general formula (7).

[Formula 7]

(In the above formula (7)

R ⁹ and R ¹¹ are each independently a hydrogen atom or a C1 to C20 alkyl group,

R ¹⁰ is a carboxyl group or CONHR (where, R is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group unsubstituted), and a, R ¹² is a carboxyl group, R ¹⁰ and R ¹² are fused together You can build a loop.)

The carboxyl group-containing acrylic copolymer (B) may further include at least one of the structural units represented by the following formulas (8) to (12).

[Formula 8]

(In the formula (8)

R ¹⁷ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

R ¹⁸ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group,

R ¹⁹ and R ²⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

(In the above formulas 8 to 12,

R ⁶ , R ⁷ , R ¹³ and R ¹⁵ are each independently a hydrogen atom or a C 1 to C 20 alkyl group,

R ⁸ is a hydrogen atom, a halogen atom or a hydroxy group,

R ¹⁴ is a substituted or unsubstituted C6 to C30 aryl group,

R ¹⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 cycloalkyl group,

m is an integer from 1 to 5.)

At least one of the structural units represented by the general formulas (8) to (12) may be contained in an amount of 1 to 50 mol% based on the total amount of the carboxyl group-containing acrylic copolymer (B).

The acid value of the carboxyl group-containing acrylic copolymer (B) may be 20 to 200 mgKOH / g.

The copolymer (A) and the carboxyl group-containing acrylic copolymer (B) including the structural unit represented by Formula 1 may be included in a weight ratio of 1: 1.5 Pa to 1: 5.

The photosensitive resin composition comprises (A) 1 to 40% by weight of a copolymer comprising the structural unit represented by the formula (1); (B) 1 to 60% by weight of the carboxyl group-containing acrylic copolymer; (C) 0.5 to 20% by weight of the photopolymerizable monomer; (D) 0.1 to 10% by weight of the photopolymerization initiator; (E) from 0.1 to 40% by weight of said dye; And (F) the solvent residue.

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; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof.

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

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

The photosensitive resin composition is excellent in heat resistance and chemical resistance, and exhibits a high numerical aperture and a high contrast ratio. Therefore, the photosensitive resin composition is excellent in hole and patterning properties and can be applied to a color filter. Especially, when a color filter is formed on a TFT array substrate Can be applied.

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, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.

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

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

The photosensitive resin composition according to one embodiment comprises (A) a copolymer comprising a structural unit represented by the following formula (1), (B) a carboxyl group-containing acrylic copolymer, (C) a photopolymerizable monomer, ) Dyes and (F) solvents.

Each component will be described in detail below.

(A) a copolymer comprising a structural unit represented by the following formula

The copolymer (A) may include a structural unit represented by the following general formula (1).

[Formula 1]

R ¹ , R ^3, and R ⁴ in Formula 1 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 Lt; / RTI >

R ² in Formula 1 may be a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.

The structural unit represented by the formula (1) may be contained in an amount of 0.05 to 50 mol%, specifically 0.1 to 30 mol%, based on the total amount of the copolymer (A). When the structural unit represented by the formula (1) is contained within the above range, a photosensitive resin composition having both excellent heat resistance, chemical resistance and color characteristics as well as excellent processability can be obtained.

The copolymer (A) comprising the structural unit represented by the formula (1) may further include at least one of the structural units represented by the following formulas (2) to (6) in addition to the structural unit represented by the formula (1).

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ in the general formulas 2 to 6 may each independently be a hydrogen atom or a C 1 to C 20 alkyl group.

R ⁸ in the above formulas 2 to 6 may be a hydrogen atom, a halogen atom or a hydroxy group.

R ¹⁰ in the above formulas 2 to 6 may be a carboxyl group or CONHR wherein R is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group and R ¹² is a carboxyl group And R < ¹⁰ > and R < ¹² > may be fused together to form a ring.

R ¹⁴ in the above formulas 2 to 6 may be a substituted or unsubstituted C6 to C30 aryl group.

R ¹⁶ in the formulas (2) to (6) may be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 cycloalkyl group.

M in formulas (2) to (6) may be an integer of 1 to 5.

The structural units represented by the above-mentioned formulas (2) to (6) are similar to the photoreactive functional groups contained in the photopolymerizable monomer to be described later, and the radicals induced by the photopolymerization initiator described later are added to the binder resin Lt; RTI ID = 0.0 > photopolymerization < / RTI >

Since the copolymer (A) further includes at least one of the structural units represented by the above formulas (2) to (6), it is possible to realize a fine pattern realizing important in a color filter manufactured by a color filter on array (COA) Chemical properties can be obtained.

At least one of the structural units represented by the above formulas (2) to (6) may be contained in an amount of 1 to 50 mol%, specifically 10 to 30 mol%, based on the total amount of the copolymer (A). When the structural unit is contained within the above range, it has excellent heat resistance and chemical resistance, is excellent in processability and pattern forming property, and has excellent color characteristics.

When the number of moles of the structural units represented by the above formulas (2) to (6) is n ¹ , n ² , n ³ , n ⁴ And in case n be represented by ^5, each structural unit is ^{0≤n 1 ≤50, 0≤n 2 ≤50,} 0≤n 3 ≤50, 0≤n 4 ≤50 ≤50 ⁵ and a mole ratio range of 1≤n may be present in the copolymer (a), specifically, ^{1≤n 1 ≤40, 1≤n 2 ≤40,} 1≤n 3 ≤40, 1≤n 4 ≤40 ≤40 ⁵ and the molar ratio of 3≤n ≪ / RTI > When the structural units represented by the above formulas (2) to (6) have the above range, developability, heat resistance and chemical resistance can be maintained at an appropriate level.

The weight average molecular weight of the copolymer (A) may be 1,000 to 100,000 g / mol, and may be 5,000 to 40,000 g / mol. When the weight average molecular weight of the copolymer (A) is within the above range, the developability of the photosensitive resin composition is excellent.

The amine value of the copolymer (A) may be 10 to 200 mg HCl / g, specifically 50 to 100 mg HCl / g. When the amine value of the copolymer (A) is within the above range, the heat resistance and chemical resistance of the photosensitive resin composition are excellent.

The copolymer (A) may be contained in an amount of 1 to 40% by weight, and more preferably 10 to 30% by weight based on the total amount of the photosensitive resin composition. When the copolymer (A) is included within the above range, the crosslinking property is good and the surface roughness is reduced, and the chemical resistance is excellent, so that the pattern peeling does not occur.

(B) a carboxyl group-containing acrylic copolymer

The acrylic copolymer may be a copolymer of a first monomer having a carboxyl group and a second monomer copolymerizable with the first monomer.

Examples of the first monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. These monomers may be used alone or in combination of two or more.

Examples of the second monomer include alkenyl aromatic compounds such as styrene,? -Methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Unsaturated carboxylic acid ester compounds, such as 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate; 2-aminoethyl acrylate, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-aminoethyl methacrylate, N-phenylmaleimide, glycol methacrylate, polyvalerolactone methacrylate, Unsaturated carboxylic acid aminoalkyl ester compounds such as dimethylaminoethyl 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; And unsaturated amide compounds such as acrylamide and methacrylamide. These compounds may be used singly or in combination of two or more.

The first monomer having a carboxyl group may be contained in an amount of 1 to 50% by weight, specifically 3 to 40% by weight, more specifically 5 to 30% by weight based on the total amount of the acrylic copolymer (B). When the first monomer is contained within the above range, the photosensitive resin composition is excellent in heat resistance and chemical resistance as well as processability.

The acrylic copolymer (B) obtained by copolymerization of the first monomer and the second monomer may include a structural unit represented by the following general formula (7).

[Formula 7]

R ⁹ and R ¹¹ in Formula 7 may each independently be a hydrogen atom or a C1 to C20 alkyl group.

And R ¹⁰ in the formula (7) is a carboxyl group or CONHR (where, R is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group unsubstituted), and, R ¹² is a carboxyl group, R ¹⁰ and R ¹² may be fused together to form a ring.

The acrylic copolymer (B) may further include at least one structural unit represented by the following general formulas (8) to (12) in addition to the structural unit represented by the general formula (7).

[Formula 8]

R ¹⁷ in Formula 8 may be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

R ¹⁸ in Formula 8 may be a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.

R ¹⁹ and R ²⁰ in Formula 8 may each independently be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

R ⁶ , R ⁷ , R ¹³ and R ¹⁵ in the general formulas (9) to (12) independently represent a hydrogen atom or a C 1 to C 20 alkyl group, and R ⁸ may be a hydrogen atom, a halogen atom or a hydroxy group.

May R ¹⁴ is aryl date a substituted or unsubstituted C6 to C30 in the above formulas 9 to 12, R ¹⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a C3 to C30 cycloalkyl group, and m may be an integer of 1 to 5.

The structural units represented by the general formulas (8) to (12) are structures similar to the photoreactive functional groups contained in the photopolymerizable monomers described later, and radicals induced by the photopolymerization initiator described later are added to form a binder resin Lt; RTI ID = 0.0 > crosslinking < / RTI >

Since the acrylic copolymer (B) further includes at least one of the structural units represented by the formulas (8) to (12), it is possible to realize a fine pattern realizing important in a color filter manufactured by a color filter on array (COA) Chemical resistance can be obtained.

At least one of the structural units represented by the above formulas (8) to (12) may be contained in an amount of 1 to 50 mol%, specifically 10 to 30 mol%, based on the total amount of the acrylic copolymer (B). When the structural unit is contained within the above range, it has excellent heat resistance and chemical resistance, is excellent in processability and pattern forming property, and has excellent color characteristics.

When the number of moles of the structural units represented by the general formulas (8) to (12) is represented by n ⁶ , n ⁷ , n ⁸ , n ⁹ and n ¹⁰ , each structural unit is 0? N ⁶ ? 50, 0? N ⁷ ? , 0≤n ⁸ ≤50, 0≤n ⁹ in a molar ratio range of ≤50 ¹⁰ ≤50 and 1≤n may be present in the acrylic copolymer (B), specifically, 1≤n ⁶ ≤40, 1≤n ^7? 40, 1? N ^8? 40, 1? N ^9? 40, and 3? N ^10? 40. When the structural units represented by the above formulas (8) to (12) have the above range, developability, heat resistance and chemical resistance can be maintained at an appropriate level.

The weight average molecular weight of the acrylic copolymer (B) may be 1,000 to 100,000 g / mol, and may be 5,000 to 40,000 g / mol. When the weight average molecular weight of the acrylic copolymer (B) is within the above range, the developability of the photosensitive resin composition is excellent.

The acid value of the acrylic copolymer (B) may be 20 to 200 mgKOH / g, and specifically, the acid value may be 50 to 180 mgKOH / g. When the acid value of the acrylic copolymer (B) is within the above range, the heat resistance and chemical resistance of the photosensitive resin composition are excellent.

The acrylic copolymer (B) may be contained in an amount of 1 to 60% by weight based on the total amount of the photosensitive resin composition, specifically, 20 to 50% by weight. When the copolymer (B) is contained within the above range, the crosslinking property is good and the surface roughness is reduced and the chemical resistance is excellent, so that the pattern peeling does not occur.

The copolymer (A) containing the structural unit represented by the formula (1) and the carboxyl group-containing acrylic copolymer (B) may be mixed with each other at a weight ratio of 1: 1.5 to 1: 5, 1: 3 by weight. When it is contained in the photosensitive resin composition in the above-mentioned ratio range, not only excellent heat resistance and chemical resistance but also excellent color characteristic and fairness can be obtained.

(C) Photopolymerization  Monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. 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.

The photopolymerizable monomer may be contained in an amount of 0.5 to 20% by weight based on the total amount of the photosensitive resin composition, specifically 5 to 20% by weight. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in reliability, and is excellent in developability in an alkaline developer.

(D) 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-crothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, Propyl thioxanthone, 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 1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.

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 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 contained in an amount of 0.1 to 10% by weight based on the total amount of the photosensitive resin composition, and may be contained in an amount of 0.3 to 5% by weight. 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.

(E) Dye

The dye may be a dye having a hue such as red, green, blue, yellow, or vilot.

Examples of the dyes include condensed polycyclic dyes such as triphenylmethane dyes, xanthene dyes, anthraquinone dyes and perylene dyes, phthalocyanine dyes and azo dyes. May be used alone, or two or more of them may be used in combination. It is preferable to use two or more kinds of them for adjusting the maximum absorption wavelength, cross point, cross talk and the like.

The dye has a solubility of a certain concentration or higher in a solvent to be described later, has excellent stability in the photosensitive resin composition, and has no fear of deterioration in resolution of a pixel.

The dye may be contained in an amount of 0.1 to 40% by weight, and more preferably 10 to 40% by weight based on the total amount of the photosensitive resin composition. When the dye is included in the above range, coloring property and developability are excellent.

(F) Solvent

The solvent may be a material which has compatibility with the two kinds of copolymers (A and B), the photopolymerizable monomer, the photopolymerization initiator and the dye but does not react.

The solvent is not particularly limited, but specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid 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 Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 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 to 90% by weight. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coatability and flatness can be maintained in a film having a thickness of 1 占 퐉 or more.

(G) other additives

The photosensitive resin composition includes malonic acid for preventing stains and spots upon application, for leveling properties, and for preventing generation of residues by undeveloped; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And other additives such as a radical polymerization initiator.

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.

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 additive can be easily adjusted according to desired properties.

Another embodiment provides a color filter manufactured using the photosensitive resin composition described above. A method of manufacturing the color filter is as follows.

The above-mentioned photosensitive resin composition was applied onto a glass substrate to which nothing had been applied and a glass substrate on which SiN _{x as a} protective film had been applied in a thickness of 500 to 1500 ANGSTROM using a suitable method such as spin coating and slit coating, To 3.4 m, respectively. After the application, light is irradiated to form a pattern necessary for the color filter. After the light is irradiated and the coating layer is treated with an alkali developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the 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, the image pattern obtained by the development can be further heated, cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

In general, the negative photosensitive resin is not easily stripped in the organic solvent, and thus may contaminate the lower layer 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 according to the embodiment is excellent in resistance to the stripping liquid of such a negative photosensitive resin, prevents contamination of the lower layer, and adhesion to the lower layer is improved.

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

Manufacturing example  1 to 3: Copolymer (A) Synthesis

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) initiator (based on 100 parts by weight of the total amount of monomers) and the monomers shown in the following Table 1 were added to a flask equipped with a cooling tube and a stirrer , And 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent (based on 100 parts by weight of the total amount of the monomers) was added thereto, and then stirring was started slowly under a nitrogen atmosphere. The reaction solution was heated to 75 캜 and stirred for 8 hours to obtain a copolymer.

The solid content concentration of each copolymer-containing solution obtained was 30% by weight, and the weight average molecular weight was as shown in Table 1 below. Here, the weight average molecular weight is an average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Production Example 1 Production Example 2 Production Example 3 Isobornyl methacrylate (% by weight) 20 20 20 Benzyl methacrylate (% by weight) 30 40 50 5-aminopentyl methacrylate (% by weight) 20 10 0 Dicyclo fentanyl methacrylate (% by weight) 30 30 30 Weight average molecular weight (g / mol) 13,000 13,500 13,500 PDI (polydispersity index) 1.6 1.6 1.7 Amine value (mg HCl / g) 105 58 0

Example  1 and 2 and Comparative example  1 to 3: Photosensitive resin composition production

Using the components shown in Table 2 below, a photosensitive resin composition was prepared as follows.

First, the photopolymerization initiator (D) was dissolved in the solvent (F), and the mixture was stirred at room temperature for 1 hour. The dye (E) was dissolved therein with stirring at room temperature for 1 hour. The copolymer (A), the carboxyl group-containing acrylic copolymer (B) and the photopolymerizable monomer (C) obtained in the above Preparation Examples 1 to 3 were added thereto and stirred at room temperature for 2 hours. Impurities were removed to prepare a photosensitive resin composition.

                                                      (Unit: g) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Copolymer (A-1) Production Example 1 10.0 - - - - (A-2) Production Example 2 - 10.0 - - - (A-3) Production Example 3 - - 10.0 - - (B) a carboxyl group-containing copolymer (B-1) NPR-1120 (MIWON CHEMICAL INDUSTRY) (acid value 138 mgKOH / g) 15.0 15.0 15.0 - - (B-2) NPR-202 (Miwon Company) (acid value 103 mgKOH / g) - - - 25.0 (B-3) NPR-1251 (MIYON CHEMICAL INDUSTRY) (acid value 171 mgKOH / g) - - - - 25.0 (C) Acrylic photopolymerizable monomer Dipentaerythritol hexaacrylate (DPHA) 5.0 5.0 5.0 5.0 5.0 (D) a photopolymerization initiator IGACURE OXE02 from Ciba Specialty Chemicals 1.5 1.5 1.5 1.5 1.5 (E) Dye Victoria Blue B (Fluka) 2.5 2.5 2.5 2.5 2.5 (F) Solvent (F-1) Propylene glycol monomethyl ether acetate (PGMEA) 47.0 47.0 47.0 47.0 47.0 (F-2) cyclohexanone 18.9 18.9 18.9 18.9 18.9 (G) Fluorine-based surfactant F-475 (DIC) 0.1 0.1 0.1 0.1 0.1

Evaluation 1: Chemical resistance evaluation

The chemical resistance and heat resistance of the photosensitive resin composition prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated as follows.

The photosensitive resin composition prepared in Examples 1 and 2 and Comparative Examples 1 to 3 was coated on a transparent circular glass substrate (bare glass) to which nothing was applied using a spin-coater (K-Spin 8, Were coated at a thickness of 3 mu m, respectively. After soft-baking at 80 ° C for 150 seconds using a hot-plate, exposure was performed at an output power of 60 mJ using an exposure machine (I10C manufactured by Nikon) At a developing temperature of 25 占 폚, a developing time of 60 seconds, a washing time of 60 seconds, and a spin-drying of 25 seconds. At this time, a 1 wt% aqueous solution of potassium hydroxide was used as the developing solution. Subsequently, hard-baking was performed in an oven at 200 ° C. for 30 minutes, and the substrate was immersed in a peeling liquid (PRS-2000 manufactured by JT Baker) at 25 ° C. for 5 minutes, and then deionized water, DIW).

The color change of the coating film prepared as described above was measured by using a colorimeter (spectrophotometer, MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), and the surface infiltration of the coating film was measured by observing the thickness change of the coating film. Respectively.

<Color change>

- When color change is weak after peeling liquid treatment: Excellent

- When the color change is in process after peeling liquid treatment: Poor

- When color change is strong after peeling liquid treatment: Bad

<Surface Infiltration>

(%) = (Thickness after peeling liquid treatment / thickness before peeling liquid treatment) * 100

Evaluation 2: Evaluation of heat resistance

Heat resistance was evaluated using the photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 in the same manner as in the above chemical resistance evaluation, and the results are shown in Table 3 below.

<Heat resistance>

- When color change is weak after 1 hour treatment in oven at 200 ℃: Excellent

- In case of color change after 1 hour treatment in oven at 200 ℃: Poor

- If color change is strong after 1 hour treatment in oven at 200 ℃: Bad

division Color change Surface invasion (retention rate) Heat resistance Example 1 Great 88% Great Example 2 Great 85% Great Comparative Example 1 Inadequate 80% Great Comparative Example 2 Bad 67% Inadequate Comparative Example 3 Bad 69% Inadequate

Referring to Table 3, in the case of the photosensitive resin compositions of Examples 1 and 2 comprising the copolymer (A) containing the structural unit represented by the formula (1) and the carboxyl group-containing acrylic copolymer (B) As compared with the case of Comparative Example 1 in which a copolymer containing no structural unit represented by Chemical Formula 1 was used and Comparative Examples 2 and 3 in which the copolymer (A) was not used, It can be confirmed that the coating film is less invaded on the surface and excellent in heat resistance.

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 (14)

(A) a copolymer comprising a structural unit represented by the following formula (1);
(B) a carboxyl group-containing acrylic copolymer;
(C) a photopolymerizable monomer;
(D) a photopolymerization initiator;
(E) a dye; And
(F) Solvent
.
[Formula 1]

(In Formula 1,
R ¹ , R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
R ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.)
The method of claim 1,
The structural unit represented by the formula (1) is contained in 0.05 to 50 mol% based on the total amount of the copolymer (A) comprising the structural unit represented by the formula (1).
The method of claim 1,
Wherein the copolymer (A) comprising the structural unit represented by the formula (1) further comprises at least one of the structural units represented by the following formulas (2) to (6).
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the above formulas 2 to 6,
R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ are each independently a hydrogen atom or a C 1 to C 20 alkyl group,
R ⁸ is a hydrogen atom, a halogen atom or a hydroxy group,
R ¹⁰ is a carboxyl group or CONHR (where, R is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group unsubstituted), and a, R ¹² is a carboxyl group, R ¹⁰ and R ¹² are fused together Ring,
R ¹⁴ is a substituted or unsubstituted C6 to C30 aryl group,
R ¹⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 cycloalkyl group,
and m is an integer of 1 to 5.)
The method of claim 3,
Wherein at least one of the structural units represented by the general formulas (2) to (6) is contained in an amount of 1 to 50 mol% based on the total amount of the copolymer (A) containing the structural unit represented by the general formula (1).
The method of claim 1,
Wherein the copolymer (A) comprising the structural unit represented by the formula (1) has a weight average molecular weight of 1,000 to 100,000 g / mol.
The method of claim 1,
Wherein the amine value of the copolymer (A) containing the structural unit represented by the formula (1) is 10 to 200 mg HCl / g.
The method of claim 1,
Wherein the carboxyl group-containing acrylic copolymer (B) comprises a structural unit represented by the following general formula (7).
(7)

(In the above formula (7)
R ⁹ and R ¹¹ are each independently a hydrogen atom or a C1 to C20 alkyl group,
R ¹⁰ is a carboxyl group or CONHR (where, R is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group unsubstituted), and a, R ¹² is a carboxyl group, R ¹⁰ and R ¹² are fused together You can build a loop.)
The method of claim 7, wherein
Wherein the carboxyl group-containing acrylic copolymer (B) further comprises at least one of the structural units represented by the following formulas (8) to (12).
[Chemical Formula 8]

(In the formula (8)
R ¹⁷ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
R ¹⁸ is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group,
R ¹⁹ and R ²⁰ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group.
[Chemical Formula 9]

[Formula 10]

(11)

[Chemical Formula 12]

(In the above formulas 9 to 12,
R ⁶ , R ⁷ , R ¹³ and R ¹⁵ are each independently a hydrogen atom or a C 1 to C 20 alkyl group,
R ⁸ is a hydrogen atom, a halogen atom or a hydroxy group,
R ¹⁴ is a substituted or unsubstituted C6 to C30 aryl group,
R ¹⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a C3 to C30 cycloalkyl group,
and m is an integer of 1 to 5.)
9. The method of claim 8,
Wherein at least one of the structural units represented by the general formulas (8) to (12) is contained in an amount of 1 to 50 mol% based on the total amount of the carboxyl group-containing acrylic copolymer (B).
The method of claim 1,
And the acid value of the carboxyl group-containing acrylic copolymer (B) is 20 to 200 mgKOH / g.
The method of claim 1,
Wherein the copolymer (A) containing the structural unit represented by the formula (1) and the carboxyl group-containing acrylic copolymer (B) are contained in a weight ratio of 1: 1.5 to 1: 5.
The method of claim 1,
In the photosensitive resin composition,
(A) 1 to 40% by weight of a copolymer including the structural unit represented by Formula 1;
(B) 1 to 60% by weight of the carboxyl group-containing acrylic copolymer;
(C) 0.5 to 20% by weight of the photopolymerizable monomer;
(D) 0.1 to 10% by weight of the photopolymerization initiator;
(E) from 0.1 to 40% by weight of said dye; And
(F) the solvent residual amount
.
The method of 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; Fluorine surfactants; A radical polymerization initiator; Or an additive of a combination thereof.
The color filter manufactured using the photosensitive resin composition of any one of Claims 1-13.