KR20120047344A - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition and a color filter using the same are provided to improve aperture ratio and contrast ratio and to efficiently apply the color filter to a thin film transistor array substrate. CONSTITUTION: A photo-sensitive resin composition includes acryl-based binder resins with structural units, photopolymerizable monomers, photopolymerizable initiators, pigments, and solvents. One structural unit is represented by chemical formula 1. Another structural unit is represented by chemical formula 2. In chemical formula 1, R1 is a hydrogen element or a C1 to C10 alkyl group; R2, R3, and R4 are identical or different and are hydrogen elements or substituted or non-substituted (meta)acrylate groups; at least one of R2, R3, and R4 is substituted or non-substituted (meta)acrylate groups; Z1, Z2, and Z3 are substituted or non-substituted C1 to C20 alkylene groups. In chemical formula 2, R20 is a hydrogen element or a C1 to C10 alkyl group; R21 is a carboxylic group, a substituted or non-substituted C1 to C20 alkyl group, or COR"COOH; and R' is a substituted or non-substituted C1 to C20 alkylene group or a substituted or non-substituted C1 to C20 alkoxylene group.

Description

PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER USING THE SAME}

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

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

The pigment dispersion method is a method for forming a colored thin film by repeating a series of processes of applying, exposing, developing and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. The pigment dispersion method can improve heat resistance and durability, which are the most important properties of the color filter, and have the advantage of keeping the thickness of the film uniform.

The manufacturing process of the color filter by the pigment dispersion method includes many chemical treatment steps. In order to maintain the pattern formed under such conditions, there is a need for a photosensitive resin for color filters capable of improving the yield of color filters with excellent chemical resistance while securing a development margin.

In addition, since the demand for high quality large screens is increasing, development of color filters with high aperture ratio and high performance is required.

One aspect of the present invention is to provide a photosensitive resin composition that is excellent in heat resistance and chemical resistance, and can exhibit high opening ratio and high contrast ratio.

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

One aspect of the present invention (A) acrylic binder resin comprising a structural unit represented by the formula (1) and a structural unit represented by the following formula (2); (B) photopolymerizable monomers; (C) photoinitiator; (D) pigments; And (E) provides a photosensitive resin composition comprising a solvent.

[Formula 1]

(In the formula 1,

R ¹ is a hydrogen atom or a C1 to C10 alkyl group,

R ² , R ³ and R ⁴ are the same as or different from each other, a hydrogen atom, or a substituted or unsubstituted (meth) acrylate, and at least one of R ² , R ³ and R ⁴ is substituted or unsubstituted (meth ) Acrylate,

Z ¹ , Z ² and Z ³ are each a substituted or unsubstituted C1 to C20 alkylene group.)

[Formula 2]

(In Formula 2,

R ²⁰ is a hydrogen atom or a C1 to C10 alkyl group,

R ²¹ is a carboxy group, a substituted or unsubstituted C1 to C20 alkyl group, or COR'COOH, wherein R 'is a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C1 to C20 alkoxylene group .)

The structural unit represented by Formula 1 may include the following Formula 3.

(3)

(3)

R ⁵ is a hydrogen atom or a C1 to C10 alkyl group.)

The structural unit represented by Chemical Formula 1 may be included in an amount of 0.05 to 50 wt% based on the total amount of the acrylic binder resin, and the structural unit represented by Chemical Formula 2 may be included in an amount of 5 to 40 wt% based on the total amount of the acrylic binder resin. have.

The acrylic binder resin may further include at least one of structural units represented by the following Chemical Formulas 4-1 to 4-5.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Chemical Formulas 4-1 to 4-5,

R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ are the same as or different from each other, are a hydrogen atom or a C1 to C10 alkyl group,

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

R ¹⁰ is 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, R ¹² is a carboxyl group, R ¹⁰ and R ¹² Are fused together to form a 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.)

The weight average molecular weight of the acrylic binder resin may be 1,000 to 150,000 g / mol, the acid value may be 20 to 200 mgKOH / g.

The photosensitive resin composition, (A) 1 to 50% by weight of the acrylic binder resin; (B) 0.1 to 40% by weight of the photopolymerizable monomer; (C) 0.1 to 20% by weight of the photopolymerization initiator; (D) 0.1 to 40% by weight of the pigment; And (E) may include the remaining amount of the solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or an additive of a combination thereof.

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

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

As the photosensitive resin composition having excellent heat resistance and chemical resistance and exhibiting high opening ratio and high contrast ratio is provided, it can be usefully applied to a color filter and the like, and particularly useful in forming a color filter on a TFT array substrate. .

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 stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, It means substituted with a substituent of C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C30 heteroaryl group or a combination thereof.

In addition, "hetero" means at least one hetero atom of at least one of N, O, S and P in the ring group unless otherwise specified in the present specification.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

The photosensitive resin composition according to one embodiment includes (A) an acrylic binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a pigment, and (E) a solvent.

Each component is demonstrated concretely below.

(A) Acrylic Binder Resin

The acrylic binder resin may include a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formula 2.

[Formula 1]

(In the formula 1,

R ¹ is a hydrogen atom or a C1 to C10 alkyl group,

R ² , R ³ and R ⁴ are the same as or different from each other, a hydrogen atom, or a substituted or unsubstituted (meth) acrylate, and at least one of R ² , R ³ and R ⁴ is substituted or unsubstituted (meth ) Acrylate,

Z ¹ , Z ² and Z ³ are each a substituted or unsubstituted C1 to C20 alkylene group.)

[Formula 2]

(In Formula 2,

R ²⁰ is a hydrogen atom or a C1 to C10 alkyl group,

R ²¹ is a carboxy group, a substituted or unsubstituted C1 to C20 alkyl group, or COR'COOH, wherein R 'is a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C1 to C20 alkoxylene group .)

The structural unit represented by Chemical Formula 1 has a double bond such as a (meth) acrylate group at at least one of R ² , R ^3, and R ⁴ , and accordingly, the sensitivity is improved, resulting in more dense film formation. Thereby, heat resistance and chemical resistance become excellent.

Examples of the structural unit represented by Chemical Formula 1 include the following Chemical Formula 3 ', but are not limited thereto.

(3)

(3)

R ⁵ is a hydrogen atom or a C1 to C10 alkyl group.)

The structural unit represented by Chemical Formula 1 may be included in an amount of 0.05 to 60% by weight, and specifically 0.1 to 40% by weight, based on the total amount of the acrylic binder resin. When the structural unit represented by Formula 1 is included in the above range, it is excellent in heat resistance, chemical resistance, and fine pattern formation.

In addition, the structural unit represented by Formula 2 may be included in 5 to 40% by weight based on the total amount of the acrylic binder resin. When the structural unit represented by Formula 2 is included in the above range, it may have excellent developability.

The acrylic binder resin may further include at least one of the structural units represented by the following Chemical Formulas 4-1 to 4-5, in addition to the structural units represented by the Chemical Formula 1 'and Chemical Formula 2.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Chemical Formulas 4-1 to 4-5,

R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ are the same as or different from each other, are a hydrogen atom or a C1 to C10 alkyl group,

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

R ¹⁰ is 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, R ¹² is a carboxyl group, R ¹⁰ and R ¹² Are fused together to form a 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.)

The structural units represented by Chemical Formulas 4-1 to 4-5 are similar in structure to photoreaction functional groups contained in the photopolymerizable monomers described below, and the radicals induced by the photopolymerization initiators described later are added to photopolymerize the acrylic binder resin. The reaction may cause crosslinking.

The structural units represented by Formulas 4-1 to 4-5 may be adjusted according to the ratio of the photopolymerizable monomer and the photopolymerization initiator described later.

The acrylic binder resin further includes at least one of the structural units represented by Chemical Formulas 4-1 to 4-5, thereby obtaining a fine pattern important in a color filter manufactured by a COA method, etc., and obtaining excellent heat and chemical resistance. have.

When the acrylic binder resin includes at least one of the structural units represented by Formulas 4-1 to 4-5, the acrylic binder resin may be included in an amount of 1 to 70% by weight based on the total amount of the acrylic binder resin, and specifically 5 to 50 It may be included in weight percent. If included in the above range can maintain the necessary developability, excellent chemical resistance and chemical resistance, excellent stability of the pattern, does not reduce the light transmission characteristics. 　

When the acrylic binder resin includes all the structural units represented by Chemical Formulas 4-1 to 4-5, the number of moles of each structural unit is n ¹ , n ² , n ³ , n ^{4, respectively.} And if the display ⁵ to n, molar ratio of the structural unit are each ^{0≤n 1 ≤50, 0≤n 2 ≤50,} 0≤n 3 ≤50, 0≤n 4 of ≤50 ≤50 ⁵ and 1≤n It may have a range, specifically 1≤n ¹ ≤40, 1≤n ² ≤40, 1≤n ³ ≤40, 1≤n ⁴ ≤40 and 3≤n ⁵ ≤40. When the structural units represented by Formulas 4-1 to 4-5 have the above ratio ranges, developability, heat resistance, and chemical resistance may be maintained at an appropriate level.

The weight average molecular weight of the acrylic binder resin may be 1,000 to 150,000 g / mol, specifically, may be 3,000 to 50,000 g / mol. When the weight average molecular weight of the said acrylic binder resin is in the said range, developability of the photosensitive resin composition is excellent.

The acid value of the acrylic binder resin may be 20 to 200 mgKOH / g, specifically, may be 50 to 160 mgKOH / g. When the acid value of the said acrylic binder resin exists in the said range, developability of the photosensitive resin composition is excellent.

The acrylic binder resin may be included in an amount of 1 to 50% by weight, and specifically 3 to 30% by weight, based on the total amount of the photosensitive resin composition. When the acrylic binder resin is included in the above range, the developability to the alkaline developer is excellent, the crosslinkability is good, the surface roughness is reduced, and the chemical resistance is excellent, so that no pattern tearing occurs.

(B) 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, the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

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 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 tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) 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.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-450 ^{® from} Toagosei Kagaku Kogyo Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nihon Kayaku Co., Ltd., KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 0.1 to 40% by weight, and specifically 1 to 30% by weight, based on the total amount of the photosensitive resin composition. In the case where the photopolymerizable monomer is included in the above range, curing is sufficiently performed at the time of exposure in the pattern forming step to provide excellent reliability and excellent developability to an alkaline developer.

(C) Light curing Initiator

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

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

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diiso Propyl thioxanthone, 2-chloro thioxanthone, etc. are mentioned.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-tri chloromethyl (Piperonyl) -6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, etc. are mentioned.

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.

In addition to the compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator may be included in an amount of 0.1 to 20% by weight, specifically 0.3 to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and it is possible to prevent a decrease in transmittance due to the unreacted initiator.

(D) Pigment

As the pigment, a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, a purple pigment, or the like can be used.

Specifically, the pigments include anthraquinone pigments, perylene pigments, phthalocyanine pigments, azo pigments, and the like, which may be used alone or in combination of two or more. Among them, two or more may be used in combination for the adjustment of the maximum absorption wavelength, the adjustment of the cross point, the cross talk, and the like.

A dispersant may be used together to disperse the pigment in the photosensitive resin composition.

Specifically, the pigment may be used after surface treatment with a dispersant in advance, or a dispersant may be added together with the pigment in preparing the photosensitive resin composition.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids. Salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more thereof.

The dispersant may be included in an amount of 0.01 to 15 wt% based on the total amount of the photosensitive resin composition. When the dispersant is included in the above range, excellent dispersibility of the photosensitive resin composition, excellent stability, developability and patternability can be obtained.

The primary particle diameter of the pigment may be 10 to 100 nm, specifically 10 to 70 nm. When the primary particle diameter of the pigment is in the above range, the stability in the pigment dispersion is excellent and the resolution of the pixel is excellent.

The pigment may be included in an amount of 0.1 to 40% by weight, specifically 0.3 to 20% by weight, based on the total amount of the photosensitive resin composition. When the said pigment is contained in the said range, the coloring property and developability of a photosensitive resin composition are excellent.

(E) solvent

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Ethylene glycols such as ethylene glycol and diethylene glycol; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl 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-n-butylkenone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxy acetic acid alkyl esters such as methyl oxy acetate, oxy ethyl acetate and oxy butyl acetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as methyl 3-oxy propionate and ethyl 3-oxypropionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate and 3-ethoxy methyl propionate; 2-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate and 2-oxy propionic acid propyl; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters, such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as methyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl butanoate; Ketone acid esters such as ethyl pyruvate and the like, and N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, High boiling point solvents, such as ethyl benzoate, diethyl oxalate, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, are mentioned.

Among them, glycol ethers such as ethylene glycol monoethyl ether, in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxy ethyl propionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol methylether acetate and propylene glycol propylether acetate can be used.

The solvent may be included in the balance relative to the total amount of the photosensitive resin composition, specifically, may be included in 20 to 90% by weight. When the solvent is included in the above range, the coating property of the photosensitive resin composition is excellent, and flatness may be maintained in a film having a thickness of 1 μm or more.

(F) 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; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; It may further include other additives such as radical polymerization initiators.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ -Glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like by BM Chemie; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. by Dai Nippon Inky Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Corporation; Asahi Grass Co., Ltd. Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc .; 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 the desired physical properties.

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

On the glass substrate on which nothing is applied, and on the glass substrate on which SiN _{x as a} protective film is applied with a thickness of 500 to 1500 kPa, the above-mentioned photosensitive resin composition is applied using a suitable method such as spin coating or slit coating. Apply each to a thickness of 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After irradiating the light, the coating layer is treated with an alkali developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. By repeating this process in accordance with the required number of R, G and B colors, a color filter having a desired pattern can be obtained.

Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.

In general, the negative photosensitive resin is not easily stripped in the organic solvent, 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  One

29.8 g of pentaerythrotriacrylate (Aldrich) and 35.43 g of propylene glycol methylethyl acetate (Daicel Chemical) were added to the reactor, and the temperature was raised to 50 ° C. Then, 6.8 g of sodium ethoxide (Aldrich) was added in small portions. 9.3 g of chlorohydrin (Aldrich Co., Ltd.) was added over 30 minutes, heated to 80 ° C., and maintained for 3 hours to prepare a compound represented by the following Formula 5.

[Chemical Formula 5]

Manufacturing example  2-1 to 2-9

In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a photopolymerization initiator and the monomers of Table 1 with respect to 100 parts by weight of the total amount of monomers in Table 1 below These were added in each weight ratio, 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was added to 100 parts by weight of the total amount of the photopolymerization initiator and the monomer, and then stirring was gradually started under a nitrogen atmosphere. The reaction solution thus obtained was heated to 80 ° C. and stirred for 8 hours to prepare each copolymer.

In this case, the weight average molecular weight of the copolymer is polystyrene reduced average molecular weight measured using GPC (Gel Permeation Chromatography), it is shown in Table 1 below.

     (Unit: wt%) Manufacturing example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 Methacrylic acid 15 15 15 20 20 20 25 25 25 Polyvalerolactone methacrylate 10 10 - 5 5 5 - - - N-phenyl maleimide 10 10 10 10 10 10 - - - Hydroxyethyl methacrylate - 10 - - 10 - - - 10 Styrene 15 15 15 15 15 15 - - - Benzyl methacrylate 40 20 20 40 20 20 75 55 55 Glycol methacrylate 10 10 10 10 10 10 - - - n-butyl methacrylate - - 10 - - 10 - 10 - Glycidyl methacrylate - - 10 - - 10 - - 10 N-vinyl pyrrolidinone - 10 10 - 10 - - 10 - Weight average molecular weight (g / mol) of the prepared copolymer 14000 13500 14000 15000 14000 16000 16000 15000 14000

Manufacturing example  3-1 to 3-9

In a flask equipped with a cooling tube and a stirrer, 100 parts by weight of each copolymer prepared in Preparation Examples 2-1 to 2-9 and 6 parts by weight of the compound prepared in Preparation Example 1 were added thereto, and then gradually under nitrogen atmosphere. Agitation was started. Each reaction solution obtained therefrom was heated to 50 ° C. and stirred for 12 hours to prepare each copolymer including the structural unit represented by the following formula (6).

In this case, the weight average molecular weight of the copolymer is shown in Table 2 as a polystyrene reduced average molecular weight measured by using GPC (Gel Permeation Chromatography).

[Formula 6]

Manufacturing example 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 Weight average molecular weight (g / mol) of the prepared copolymer 14500 14000 14500 15500 14500 16500 16500 15500 14500

Example  1 to 9: preparing photosensitive resin composition

0.2 g of the following photopolymerization initiator was dissolved in 38.4 g of the solvent and stirred at room temperature for 2 hours. Then, 8.0 g of each of the copolymers prepared in Preparation Examples 3-1 to 3-9 was used as an acrylic binder resin. 4.5 g of the photopolymerizable monomer and 0.1 g of the following additive were added and stirred at room temperature for 2 hours. Subsequently, 48.8 g of the following pigment dispersion was added to each of the obtained reaction products, followed by stirring at room temperature for 1 hour. Subsequently, each obtained product was filtered three times to remove impurities, thereby preparing each photosensitive resin composition according to Examples 1-9.

Comparative example  1 to 9: preparing photosensitive resin composition

Except for using the respective copolymers prepared in Preparation Examples 2-1 to 2-9 as the acrylic binder resin in Examples 1 to 9, each of the photosensitive resin composition according to Comparative Examples 1 to 9 was prepared. .

(A) Acrylic Binder Resin: Copolymers prepared in Preparation Examples 3-1 to 3-9 and copolymers prepared in Preparation Examples 2-1 to 2-9, respectively, were used.

(B) Photopolymerizable monomer: Dipentaerythritol hexaacrylate was used.

(C) Photoinitiator: IRGACURE OXE02 from CIBA-GEIGY was used.

(D) Pigment dispersion: 6.2 g of red pigment (BT-CF from Ciba Specialty Chemicals), 2.8 g of yellow pigment (2RP-CF from Ciba Specialty Chemicals), 3.4 g of dispersant (BYK163 from BYK), carboxylic acid / A pigment dispersion consisting of 3.4 g of benzyl methacrylate copolymer (NPR8000 from Miwon Corporation) and 30.0 g of propylene glycol methylether acetate was used.

(E) Solvent: 26 g of propylene glycol methylether acetate and 12.4 g of ethylethoxy propionate were used in combination.

(F) Additive: As a fluorine-type surfactant, F-475 from DIC Corporation was used.

Evaluation 1: Stripper  Immunity assessment

Using each photosensitive resin composition prepared in Examples 1 to 9 and Comparative Examples 1 to 9, peeling solution resistance evaluation was performed by the following method.

Using a spin-coater (K-Spin8 from KDNS), the silicon nitride (SiN _x ) is coated on a transparent bare glass on which nothing is applied, and a silicon nitride (SiN _x ) is 500Å thick. On the glass substrate, each of the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9 was applied to a thickness of 3 µm, respectively. After soft-baking at 80 ° C for 150 seconds using a hot-plate and exposing at 60mJ power using an exposure machine (I10C manufactured by Nikon), the developer The developing temperature was 25 ° C., a developing time of 60 seconds, a washing time of 60 seconds, and spin-drying for 25 seconds. At this time, a 1% by weight aqueous potassium hydroxide solution was used as the developer. Thereafter, the mixture was hard-baked for 30 minutes in an oven at 230 ° C., immersed in a 70 ° C. stripping solution (PRS-2000 manufactured by JTBaker) for 10 minutes, and then deionized water (DIW). ) And dried.

The color change (ΔE) of each photosensitive resin composition coating film prepared by the above method was measured using a colorimeter (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), and the peeling state was observed by using an optical microscope. As shown in Table 3 below.

<Color change>

-Color change (△ E) less than 3: excellent

-Color change (△ E) is more than 3 and less than 5: insufficient

-Color change (△ E) is 5 or more:

<Relaxed state>

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

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

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

Evaluation 2: heat resistance evaluation

Using each photosensitive resin composition prepared in Examples 1 to 9 and Comparative Examples 1 to 9, heat resistance evaluation was performed in the following manner.

Using a spin-coater (K-Spin8 from KDNS), the silicon nitride (SiN _x ) is coated on a transparent bare glass on which nothing is applied, and a silicon nitride (SiN _x ) is 500Å thick. On the glass substrates, the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9 were respectively applied to a thickness of 3 μm. After soft-baking at 80 ° C for 150 seconds using a hot-plate and exposing at 60mJ power using an exposure machine (I10C manufactured by Nikon), the developer The developing temperature was 25 ° C., a developing time of 60 seconds, a washing time of 60 seconds, and spin-drying for 25 seconds. At this time, a 1% by weight aqueous potassium hydroxide solution was used as the developer. Thereafter, after hard-baking (hard-baking) for 30 minutes in an oven at 230 ° C., the color was measured, and after baking for 2 hours in an oven at 230 ° C., color change (ΔE) was measured. Measured using a colorimeter (MCPD3000, Otsuka Electronics, Inc.), the results are shown in Table 3 below.

<Heat resistance>

-Color change (△ E) less than 3: excellent

-Color change (△ E) is more than 3 and less than 5: insufficient

-Color change (△ E) is 5 or more:

division Stripper resistance Heat resistance Color change Peeling state bare glass SiN _x bare glass SiN _x bare glass SiN _x Example 1 Great Great Great Great Great Great Example 2 Great Great Great Great Great Great Example 3 Great Great Great Great Inadequate Inadequate Example 4 Great Great Great Great Great Great Example 5 Great Great Inadequate Inadequate Great Great Example 6 Great Great Great Great Inadequate Inadequate Example 7 Great Great Great Great Great Great Example 8 Great Great Inadequate Inadequate Inadequate Inadequate Example 9 Great Great Great Great Great Great Comparative Example 1 Great Great Bad Bad Inadequate Inadequate Comparative Example 2 Bad Bad Bad Bad Bad Bad Comparative Example 3 Bad Bad Inadequate Inadequate Bad Bad Comparative Example 4 Bad Great Bad Bad Bad Bad Comparative Example 5 Bad Bad Inadequate Bad Bad Bad Comparative Example 6 Bad Bad Great Bad Bad Bad Comparative Example 7 Bad Bad Bad Bad Great Great Comparative Example 8 Great Inadequate Inadequate Bad Inadequate Bad Comparative Example 9 Bad Bad Bad Bad Great Great

Referring to Table 3, in Examples 1 to 9 using the acrylic binder resin containing a structural unit of formula 1 according to an embodiment, Comparative Example 1 using an acrylic binder resin not containing a structural unit of formula 1 Compared with the case of 9 to 9, it can be confirmed that there is little color change with respect to the peeling liquid process, there is no peeling of a coating film, and it is 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 (10)

(A) an acrylic binder resin comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2);
(B) photopolymerizable monomers;
(C) photoinitiator;
(D) pigments; And
(E) solvent
Photosensitive resin composition comprising a.
[Formula 1]

(In Formula 1,
R ¹ is a hydrogen atom or a C1 to C10 alkyl group,
R ² , R ³ and R ⁴ are the same as or different from each other, a hydrogen atom, or a substituted or unsubstituted (meth) acrylate, and at least one of R ² , R ³ and R ⁴ is substituted or unsubstituted (meth ) Acrylate,
Z ¹ , Z ² and Z ³ are each a substituted or unsubstituted C1 to C20 alkylene group.)
(2)

(In the formula (2)
R ²⁰ is a hydrogen atom or a C1 to C10 alkyl group,
R ²¹ is a carboxy group, a substituted or unsubstituted C1 to C20 alkyl group, or COR'COOH, wherein R 'is a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C1 to C20 alkoxylene group .)
The method of claim 1,
The structural unit represented by the formula (1) is a photosensitive resin composition comprising the formula (3).
(3)

(In Chemical Formula 3,
R ⁵ is a hydrogen atom or a C1 to C10 alkyl group.)
The method of claim 1,
The structural unit represented by Formula 1 is contained in 0.05 to 50% by weight based on the total amount of the acrylic binder resin.
The method of claim 1,
The structural unit represented by the formula (2) is 5 to 40% by weight based on the total amount of the acrylic binder resin photosensitive resin composition for color filters.
The method of claim 1,
The acrylic binder resin further comprises at least one of the structural units represented by the following formula 4-1 to 4-5.
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Chemical Formulas 4-1 to 4-5,
R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ are the same as or different from each other, are a hydrogen atom or a C1 to C10 alkyl group,
R ⁸ is a hydrogen atom, a halogen atom or a hydroxy group,
R ¹⁰ is 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, R ¹² is a carboxyl group, R ¹⁰ and R ¹² Are fused together to form a 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.)
The method of claim 1,
The weight average molecular weight of the acrylic binder resin is 1,000 to 150,000 g / mol of the photosensitive resin composition.
The method of claim 1,
The acid value of the acrylic binder resin is 20 to 200 mgKOH / g photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition,
(A) 1 to 50% by weight of the acrylic binder resin;
(B) 0.1 to 40% by weight of the photopolymerizable monomer;
(C) 0.1 to 20% by weight of the photopolymerization initiator;
(D) 0.1 to 40% by weight of the pigment; And
(E) the solvent residual amount
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or an additive of a combination thereof.
The color filter manufactured using the photosensitive resin composition of any one of Claims 1-9.