KR102243364B1 - Photosensitive resin composition, photosensitive resin layer using the same, color filter and display device - Google Patents

Abstract

(A) binder resin; (B) A bifunctional (meth)acrylate-based monomer, a six-functional (meth)acrylate-based monomer, and the six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal are formed by polymerization reaction A photopolymerizable compound containing the monomer; (C) a photoinitiator; (D) a colorant and (E) a solvent, and the monomer produced by the polymerization reaction between the six-functional (meth)acrylate-based monomer and the monomer having four thiol groups at the terminal is 14 weight based on the total amount of the photopolymerizable compound A photosensitive resin composition contained in% to 30% by weight, a photosensitive resin film prepared using the photosensitive resin composition, a color filter and a display device including the same are provided.

Description

Photosensitive resin composition, photosensitive resin film manufactured using the same, color filter, and display device {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME, COLOR FILTER AND DISPLAY DEVICE}

The present description relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, a color filter, and a display device.

A liquid crystal display device, which is one of the display devices, has advantages of light weight, thinness, low cost, low power consumption, and excellent integration with integrated circuits, and thus its use range is expanding for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a color filter in which unit pixels in which subpixels of red (R), green (G), and blue (B) corresponding to the three primary colors of light are set are repeatedly formed. When the brightness is controlled by applying a color signal to each sub-pixel in a state in which each sub-pixel is arranged adjacent to each other, a specific color is displayed in the unit pixel by the synthesis of the three primary colors.

The color filter is made of dyes or pigments of red (R), green (G), and blue (B), and this dye material serves to change the white light of the backlight unit into respective colors. The spectrum of the dye material is improved as there is no unnecessary wavelength other than the required absorption wavelength and has a narrow absorption band. In addition, it must have excellent heat resistance, light resistance, and chemical resistance that does not fade or discolor under UV, acid, and basic conditions exposed during the etching process of the color resist.

The adhesion to the lower substrate capable of maintaining the pattern characteristics under severe conditions in the process occupies an important position among the characteristics that the color resist must secure. As a method of improving adhesion, various methods such as application of additives having good adhesion to the lower substrate, change of the kind of photopolymerizable compound, and application of a binder resin having good adhesion are applied, but the adhesion to the lower substrate is applied. When this good additive is applied, a problem of residues leaving an undeveloped part occurs, and a change in the kind of the photopolymerizable compound affects the pattern sensitivity and developability, resulting in a problem that does not satisfy the basic pattern characteristics.

Accordingly, efforts to develop a photosensitive resin composition for a color filter in which adhesion is maximized while maintaining basic pattern characteristics such as sensitivity, developability, and residue are being continued.

One embodiment is to provide a photosensitive resin composition capable of improving adhesion while maintaining pattern characteristics without residue.

Another embodiment is to provide a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment is to provide a color filter including the photosensitive resin film.

Another embodiment is to provide a display device including the color filter.

One embodiment of the present invention is (A) a binder resin; (B) A bifunctional (meth)acrylate-based monomer, a six-functional (meth)acrylate-based monomer, and the six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal are formed by polymerization reaction A photopolymerizable compound containing the monomer; (C) a photoinitiator; (D) a colorant and (E) a solvent, and the monomer produced by the polymerization reaction between the six-functional (meth)acrylate-based monomer and the monomer having four thiol groups at the terminal is 14 weight based on the total amount of the photopolymerizable compound It provides a photosensitive resin composition contained in% to 30% by weight.

The bifunctional (meth)acrylate-based monomer may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group,

m and n are each independently an integer of 1 to 10, but 11≦m+n≦20.

The six-functional (meth) acrylate-based monomer may be dipentaerythritol hexaacrylate.

The six-functional (meth) acrylate-based monomer and the six-functional (meth) acrylate-based monomer and the monomers produced by polymerization between the monomer having four thiol groups at the terminal are each independently the bifunctional (meth) It may be included in a higher content than the acrylate-based monomer.

The six-functional (meth) acrylate-based monomer may be included in an amount higher than that of a monomer generated by a polymerization reaction between the six-functional (meth) acrylate-based monomer and a monomer having four thiol groups at the terminal.

The colorant may include a green pigment and a yellow pigment.

The green pigment is a green pigment C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62 or combinations thereof.

The yellow pigment is C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. Pigment Yellow 215, C.I. Pigment Yellow 231 or combinations thereof.

The binder resin may be an acrylic binder resin.

The acrylic binder resin may have a weight average molecular weight of 5000 g/mol to 15000 g/mol.

The acrylic binder resin may have an acid value of 80 mgKOH/g to 130 mgKOH/g.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) binder resin 1% by weight to 10% by weight; (B) 1% to 10% by weight of the photopolymerizable compound; (C) 0.1% to 5% by weight of the photopolymerization initiator; It may include 30% to 60% by weight of the (D) colorant and 30% to 60% by weight of the solvent (E).

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; And at least one additive selected from radical polymerization initiators.

Another embodiment provides a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

Another embodiment provides a display device including the color filter.

The display device may be a liquid crystal display (LCD).

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

The photosensitive resin composition according to an embodiment replaces some of the previously applied photopolymerizable compounds with other types, and limits their content, while maintaining basic pattern characteristics such as sensitivity, developability, and residue. A color filter in which adhesion is maximized and a display device including the color filter may be provided.

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

Unless otherwise specified in the specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional groups of the present invention is a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group ( NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and each independently a C1 to C10 alkyl group), an amidino group, A hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and It means substituted with one or more substituents selected from the group consisting of substituted or unsubstituted heterocyclic groups.

Unless otherwise specified in the specification, “alkyl group” refers to a C1 to C20 alkyl group, specifically C1 to C15 alkyl group, and “cycloalkyl group” refers to a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" refers to a C1 to C20 alkoxy group, specifically C1 to C18 alkoxy group, and "aryl group" refers to a C6 to C20 aryl group, specifically C6 to It means a C18 aryl group, "alkenyl group" means a C2 to C20 alkenyl group, specifically C2 to C18 alkenyl group, and "alkylene group" means a C1 to C20 alkylene group, specifically C1 It means a to C18 alkylene group, "arylene group" means a C6 to C20 arylene group, and specifically, it means a C6 to C16 arylene group.

Unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid" It means both are possible.

In the present specification, unless otherwise defined, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formula in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

In addition, unless otherwise defined in the specification, "*" means a part connected to the same or different atoms or chemical formulas.

One embodiment is (A) a binder resin; (B) A bifunctional (meth)acrylate-based monomer, a six-functional (meth)acrylate-based monomer, and the six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal are formed by polymerization reaction A photopolymerizable compound containing the monomer; (C) a photoinitiator; (D) a colorant and (E) a solvent, and the monomer produced by the polymerization reaction between the six-functional (meth)acrylate-based monomer and the monomer having four thiol groups at the terminal is 14 weight based on the total amount of the photopolymerizable compound It provides a photosensitive resin composition contained in% to 30% by weight.

Adhesion with the lower substrate capable of maintaining the pattern characteristics under severe conditions in the color filter process is one of the important characteristics that the color resist must secure. In general, when the adhesion is improved, the adhesion to the lower substrate is strengthened, resulting in a residual issue in which an undeveloped part remains. In addition, when the type of the photopolymerizable compound is changed, the pattern sensitivity and developability may be affected and the basic pattern characteristics may not be satisfied. According to an embodiment, for a color filter that can maximize adhesion to the lower substrate while maintaining basic pattern characteristics such as sensitivity, developability, and residue by changing some of the types of the existing applied photopolymerizable compound and limiting its content ( Or for a display device) photosensitive resin composition can be provided.

Hereinafter, each component will be described in detail.

(A) binder resin

The binder resin may include an acrylic binder resin.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer 　 and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including at least one acrylic repeating unit.

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

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

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide; And the like, and these may be used alone or in combination of two or more.

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

The weight average molecular weight of the binder resin may be 5,000 g/mol to 15,000 g/mol, for example, 7,000 g/mol to 120,000 g/mol. In addition, the acid value of the binder resin may be 80 mgKOH/g to 130 mgKOH/g. When the weight average molecular weight and acid value of the binder resin are within the above ranges, the photosensitive resin composition has excellent physical and chemical properties, has an appropriate viscosity, and has excellent adhesion to a substrate when manufacturing a color filter.

The binder resin may be included in an amount of 1% to 10% by weight, such as 3% to 7% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, developability is excellent and crosslinking property is improved when manufacturing a color filter, so that excellent surface smoothness can be obtained.

(B) Photopolymerization compound

The photosensitive resin composition according to an embodiment includes a bifunctional (meth)acrylate-based monomer (first monomer), a six-functional (meth)acrylate-based monomer (second monomer), and the six-functional (meth)acrylate A polymerization reaction between the six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal, including a monomer (third monomer) produced by polymerization between a system monomer and a monomer having 4 thiol groups at the terminal The resulting monomer (third monomer) is contained in an amount of 14% to 30% by weight based on the total amount of the photopolymerizable compound.

For example, as the first monomer and the second monomer, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond may be used. Since the first monomer and the second monomer have the ethylenically unsaturated double bond, sufficient polymerization occurs during exposure in the 　 pattern formation process, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.

Conventionally, a six-functional (meth)acrylate-based monomer was used alone as a photopolymerizable compound, but according to one embodiment, the six-functional (meth)acrylic, together with the six-functional (meth)acrylate-based monomer A monomer (third monomer) generated by polymerization between a rate-based monomer and a monomer having four thiol groups at the terminal is additionally included, and in addition, the third monomer is 14% to 30% by weight based on the total amount of the photopolymerizable compound By being included in %, it is possible to provide a photosensitive resin composition capable of maximizing adhesion to a lower substrate without generating a residue issue.

When the third monomer is included in an amount of less than 14% by weight based on the total amount of the photopolymerizable compound, adhesion with the lower substrate cannot be improved, and when the third monomer is included in an amount of more than 30% by weight based on the total amount of the photopolymerizable compound, adhesion However, there is a problem that a residual issue occurs.

In addition, the photopolymerizable monomer should contain all of the first monomer, the second monomer, and the third monomer, and if any of them is not included, pattern characteristics such as residues and adhesion are deteriorated.

The bifunctional (meth)acrylate-based monomer (first monomer) may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group,

m and n are each independently an integer of 1 to 10, but 11≦m+n≦20.

For example, in Formula 1, R ¹ and R ² may each independently be a hydrogen atom, L ¹ and L ² may each independently be an unsubstituted C2 to C5 alkylene group, and m+n is 15 to 20 It may be an integer of, for example, an integer of 17.

When the photopolymerizable compound contains the bifunctional (meth)acrylate-based monomer (first monomer), developability can be improved. When the bifunctional (meth)acrylate-based monomer (first monomer) is not included, the development time is prolonged, resulting in a problem of deteriorating pattern characteristics.

Examples of the six-functional (meth)acrylate-based monomer (second 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, penta Erythritol 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 monomethyl ether (meth) Acrylate, trimethylol propane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

For example, a commercially available product of the six-functional (meth)acrylate-based monomer (second monomer) is 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 ®} of Nihon Kayaku Co., Ltd., TC-120S ^®, etc.; 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 ®} of Nihon Kayaku Co., Ltd., HX-220 ^® , R-604 ^®, etc.; Osaka Yuki Kagaku High School Co., Ltd.'s V-260 ^® , V-312 ^® , and V-335 HP ^® are listed. 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 ^® -710, Dong M-8030 ^®, same 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 Yuki Kayaku High School Co., Ltd.'s V-295 ^® , East-300 ^® , East-360 ^® , East-GPT ^® , East-3PA ^® , and East-400 ^® are listed. The above products can be used alone or in combination of two or more.

For example, the six-functional (meth) acrylate-based monomer (second monomer) may be dipentaerythritol hexaacrylate (DPHA).

The six-functional (meth) acrylate-based monomer (second monomer) and the six-functional (meth) acrylate-based monomer and a monomer (third monomer) produced by a polymerization reaction between a monomer having four thiol groups at the terminal Each independently may be included in an amount higher than that of the bifunctional (meth)acrylate-based monomer (first monomer). In addition, the six-functional (meth) acrylate-based monomer (second monomer) is a monomer (third monomer) produced by a polymerization reaction between the six-functional (meth) acrylate-based monomer and a monomer having four thiol groups at the terminal ) Can be contained in a higher content. When the order of contents between the first monomer, the second monomer, and the third monomer is as described above (the second monomer> the third monomer> the first monomer), adhesion can be improved while maintaining good pattern characteristics.

The photopolymerizable compound may be used after treatment with an acid anhydride in order to impart better developability.

The photopolymerizable compound may be included in an amount of 1% to 10% by weight, such as 3% to 7% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, hardening occurs sufficiently during exposure in the pattern formation process, thereby providing excellent reliability and excellent developability in an alkali developer.

(C) Light polymerization Initiator

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof. Can be used.

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, and the like.

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

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chlorothioxanthone.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 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-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (Trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. are mentioned.

Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one Etc. can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O- Acetate, etc. are mentioned.

In addition to the above compounds, the photopolymerization initiator may be a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, or a fluorene-based compound.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and becoming excited and then transferring the energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 0.1% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to unreacted initiators. It is possible to prevent a decrease in transmittance.

(D) colorant

The colorant may include a pigment such as a green pigment and a yellow pigment.

The green pigment is a green pigment C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62 or combinations thereof.

The yellow pigment is C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. Pigment Yellow 215, C.I. Pigment Yellow 231 or combinations thereof.

A dispersant may be used together to disperse the green pigment and the yellow pigment. Specifically, the pigment may be previously surface-treated with a dispersant, or may be used by adding a dispersant together with the pigment when preparing the composition.

Nonionic dispersants, anionic dispersants, cationic dispersants, and the like may be used as the dispersant. Specific examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylate , Alkyl amide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

Examples of commercially available products of the above dispersant are BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemical; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are PB711 and PB821 of Ajinomoto.

The 　 dispersant may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, stability, developability, and patternability are excellent in manufacturing a black column spacer according to the excellent dispersibility of the composition.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used after the pretreatment, the average particle diameter of the pigment can be refined.

The pretreatment may be performed by kneading the pigment together with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be performed at a temperature of 40° C. to 100° C., and the filtration and washing may be performed by washing the inorganic salt with water and then filtering.

Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed so that the pigment can be easily pulverized, examples of which include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. Alkylene glycol monoalkyl ether; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and these may be used alone or in combination of two or more.

The pigment that has undergone the kneading step may have an average particle diameter of 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent, and there is no fear of lowering the resolution of the pixel.

As a solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like may be used.

Specifically, the pigment may be used in the form of a pigment dispersion comprising the dispersant and a solvent to be described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid pigment may be included in an amount of 5% to 20% by weight, such as 8% to 15% by weight, based on the total amount of the pigment dispersion.

The colorant may be included in an amount of 30% to 60% by weight, such as 40% to 50% by weight, based on the total amount of the photosensitive resin composition. When the colorant is used within the above range, high luminance can be expressed in a desired color coordinate.

(E) solvent

The solvent may have compatibility with a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a colorant according to an embodiment, but materials that do not react may be used.

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; Glycol ethers such as ethylene glycol monomethyl ether and ethylene 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 methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl 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-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactate esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 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-oxypropionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionate 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, 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; Ketone acid esters such as ethyl pyruvate, and the like, and N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, in consideration of compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and ketones such as cyclohexanone may be used.

The solvent may be included in a balance, such as 30% to 60% by weight, such as 40% to 50% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus processability is excellent in manufacturing a color filter.

(F) other additives

The photosensitive resin composition may include malonic acid in order to prevent spots or spots during application, to improve leveling performance, and to prevent generation of residues due to undeveloped images; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Surfactants; And at least one additive selected from radical polymerization initiators.

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

The coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., and these may be used alone or in two or more It can be mixed and used.

Specifically, the silane-based coupling agent may be used in an amount of 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

In addition, the photosensitive resin composition for a color filter may further include a surfactant, such as a fluorine-based surfactant, if necessary, in order to further improve adhesion to the lower substrate.

Examples of the fluorine-based surfactant include DIC's F-482, F-484, and F-478, but are not limited thereto.

The surfactant is preferably contained in an amount of 0.01% to 5% by weight and more preferably 0.01% to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range, it is not preferable because there may be a problem that foreign matters are generated after development.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair physical properties.

According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment is provided.

Another embodiment provides a color filter including the above-described photosensitive resin film and a display device (eg, a liquid crystal display (LCD)) including the color filter.

The manufacturing method of the color filter is as follows.

A photosensitive resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.5 µm to 10 µm using a suitable method such as spin coating, roller coating, and spray coating on the glass substrate.

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

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

(Synthesis of photosensitive resin composition)

Example One, Example 2 and Comparative example 1 to Comparative example 5

The components mentioned below were mixed in the composition shown in Table 1 to prepare a photosensitive resin composition according to Examples 1 to 8 and Comparative Examples 1 to 5.

Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature, and then a binder resin and a photopolymerizable compound were added thereto, followed by stirring at room temperature. Then, a colorant and other additives were added to the obtained reaction product and stirred at room temperature. Subsequently, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: wt%) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) binder resin 4 4 4 4 4 4 4 (B) photopolymerizable compound B-1 3.94 3.25 3.20 2.46 4.68 - 4.00 B-2 0.74 1.43 1.48 2.22 - 4.68 0.68 B-3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 (C) photopolymerization initiator 0.29 0.29 0.29 0.29 0.29 0.29 0.29 (D) colorant D-1 31 31 31 31 31 31 31 D-2 15 15 15 15 15 15 15 (E) solvent 44.58 44.58 44.58 44.58 44.58 44.58 44.58 (F) other additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2

(A) binder resin

(A)/(B)=15/85 (w/w), molecular weight (Mw)=9,000 g/mol, acid value=110 mgKOH/g, (A): methacrylic acid, (B): benzyl methacrylate

(B) Photopolymerization compound

(B-1) Dipentaerythritol hexaacrylate (DPHA) (Japan Explosives Co., Ltd.)

(B-2) Sirius-501 (Osakayuki company)

(B-3) A-BPE-20 (Shin-nakamura company)

(C) Light polymerization Initiator

Oxime compound (IRGARCURE OXE01, BASF company)

(D) colorant

(D-1) Green pigment dispersion (C.I. Pigment Green 58, SKC company)

(D-2) Yellow pigment dispersion (C.I. Pigment Yellow 138, ENF company)

(E) solvent

Propylene glycol monomethyl ether acetate (Sigma-Aldrich Co., Ltd.)

(F) other additives

Surfactant (F-554, DIC Corporation)

Evaluation: adhesion and pattern characteristics

The photosensitive resin composition prepared in Examples 1 and 2 and Comparative Examples 1 to 5 was prepared in a thickness of 1 µm to 3 µm on a degreasing and washed glass substrate with a thickness of 1 mm. And dried on a hot plate at 90° C. for 2 minutes to obtain a coating film. Subsequently, a high-pressure mercury lamp having a dominant wavelength of 365 nm was used on the coating film, and the entire ^{surface was exposed under the condition of 60 mJ/cm 2} , and then a development was carried out to show the pattern. The developer was used by diluting the KOH solution of Hoemyung's company, and the time (seconds) of the pattern appearance was measured. Pattern formation was completed by drying (post-baking) the pattern substrate on which the development was completed in an oven at 230° C. for 20 minutes. The completed pattern was zoomed 500 times through an optical microscope, and the line size of the wide 100 μm pattern was measured, and the results are shown in Table 2 below. The residue was evaluated by visually checking the degree to which the undeveloped portion remains on the substrate after development, and the results are shown in Table 2 below.

Residue Characteristics evaluation criteria

○: There is no undeveloped part

△: The undeveloped part is visually confirmed at the edge part (thick part)

Ⅹ: Overall, a number of undeveloped parts were visually confirmed.

CD after development CD after post-baking Development time (seconds) Adhesion (line size (㎛)) Residue Example 1 105.40 105.55 17 14 ○ Example 2 105.45 105.63 18.3 12 ○ Comparative Example 1 105.91 105.65 20.4 9 △ Comparative Example 2 105.91 105.91 22 5 X Comparative Example 3 105.14 105.40 16.1 20 ○ Comparative Example 4 106.50 107.12 35 3 X Comparative Example 5 105.26 105.50 16.5 16 ○

From Table 2, the compound according to an embodiment uses three kinds of monomers as a photopolymerizable compound, and among the three kinds of monomers, between a six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal By limiting the content so that the monomer produced by the polymerization reaction is included in 14% to 30% by weight based on the total amount of the photopolymerizable compound, sensitivity and pattern characteristics are maintained without delaying the development time, and adhesion can be improved at the same time. can confirm. In general, when the adhesion is improved, the possibility of causing a residue issue increases. According to an embodiment, it can be confirmed that the adhesion is improved and no residue issue occurs. (In Table 2 above, if the adhesive force has a value of 15 or less, it can be considered that good product mass production is possible)

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to implement various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings. It is natural to fall within the scope of the invention.

Claims (17)

(A) binder resin;
(B) A bifunctional (meth)acrylate-based monomer, a six-functional (meth)acrylate-based monomer, and the six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal are formed by polymerization reaction A photopolymerizable compound containing the monomer;
(C) a photoinitiator;
(D) a colorant and
(E) contains a solvent,
A photosensitive resin composition comprising 14% by weight to 30% by weight of a monomer produced by polymerization between the six-functional (meth)acrylate-based monomer and a monomer having four thiol groups at the terminal.
The method of claim 1,
The bifunctional (meth)acrylate-based monomer is a photosensitive resin composition represented by the following Formula 1:
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group,
m and n are each independently an integer of 1 to 10, but 11≦m+n≦20.
The method of claim 1,
The six-functional (meth) acrylate-based monomer is dipentaerythritol hexaacrylate photosensitive resin composition.
The method of claim 1,
The six-functional (meth) acrylate-based monomer and the six-functional (meth) acrylate-based monomer and the monomers produced by polymerization between the monomer having four thiol groups at the terminal are each independently the bifunctional (meth) Photosensitive resin composition contained in a higher content than the acrylate-based monomer.
The method of claim 4,
The six-functional (meth) acrylate-based monomer is contained in a higher content than the monomer produced by polymerization between the six-functional (meth) acrylate-based monomer and a monomer having four thiol groups at the terminal.
The method of claim 1,
The colorant photosensitive resin composition comprising a green pigment and a yellow pigment.
The method of claim 6,
The green pigment is a photosensitive resin composition comprising a green pigment CI pigment green 7, CI pigment green 36, CI pigment green 37, CI pigment green 58, CI pigment green 59, CI pigment green 62, or a combination thereof.
The method of claim 6,
The yellow pigment is CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199, CI Pigment Yellow 215, CI Pigment Yellow 231, or a photosensitive resin composition comprising a combination thereof.
The method of claim 1,
The binder resin is an acrylic binder resin photosensitive resin composition.
The method of claim 9,
The acrylic binder resin is a photosensitive resin composition having a weight average molecular weight of 5000 g/mol to 15000 g/mol.
The method of claim 9,
The acrylic binder resin is a photosensitive resin composition having an acid value of 80 mgKOH / g to 130 mgKOH / g.
The method of claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
(A) 1% to 10% by weight of the binder resin;
(B) 1% to 10% by weight of the photopolymerizable compound;
(C) 0.1% to 5% by weight of the photopolymerization initiator;
30% to 60% by weight of the colorant (D), and
30% to 60% by weight of the solvent (E)
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; And at least one additive selected from radical polymerization initiators.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 13.
A color filter comprising the photosensitive resin film of claim 14.
A display device comprising the color filter of claim 15.
The method of claim 16,
The display device is a display device that is a liquid crystal display (LCD).