CN108107674A - Photosensitive polymer combination and use its photo-sensitive resin and colored filter - Google Patents

Abstract

The present invention provides a photosensitive resin composition, a photosensitive resin layer using the photosensitive resin composition and a color filter manufactured using the photosensitive resin composition, the photosensitive resin composition The composition comprises: (A1) a first acrylic binder resin; (A2) a second acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; and (E) a solvent. The photosensitive resin composition provided by the present invention can improve heat resistance, brightness, surface wrinkles, developing water spot, and thus can be applied to color filters.

Description

Photosensitive resin composition, photosensitive resin layer and color filter using the same

technical field

The present invention relates to a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter including the photosensitive resin layer.

Background technique

Recently, as the use of large-screen liquid crystal displays (LCDs) has remarkably increased, it has thus become increasingly necessary to improve performance thereof. Since a color filter is the most important factor for realizing color among many components of a liquid crystal display, active research is being conducted on increasing the process margin of the color filter to improve productivity.

In addition, in order to increase the color purity of a large-screen liquid crystal display (LCD), a color filter is manufactured using a photosensitive resin composition prepared by increasing the concentration of a colorant. Therefore, the photosensitive resin composition is required to have a reduced developing rate to improve productivity and yield in a manufacturing process, and to have excellent sensitivity despite light exposure.

A color filter in which three or more colors are coated on a transparent substrate is manufactured using a photosensitive resin composition through drying, electrophoretic deposition (EPD), printing, pigment dispersion, and the like. Recently, the pigment dispersion method has been more actively employed.

On the other hand, a color filter manufactured using a pigment-type photosensitive resin composition has limitations in deteriorating brightness and contrast due to the size and cohesion of pigment particles. In order to improve these limitations, studies have been conducted on dye-type photosensitive resin compositions containing a dye that does not form particles or a dye that has a primary particle diameter much smaller than that of a pigment dispersion. However, dye-type photosensitive resin compositions have poor heat resistance, light resistance, and chemical resistance, and may still be difficult to achieve commercial application.

Contents of the invention

Embodiments of the present invention provide a photosensitive resin composition capable of improving brightness, water stain generation and pattern flowing-down.

An embodiment of the present invention provides a photosensitive resin composition comprising: (A1) a first acrylic binder resin comprising a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2 , a repeating unit represented by Chemical Formula 3 and a repeating unit represented by Chemical Formula 4; (A2) a second acrylic binder resin comprising a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 5, represented by Chemical Formula 6 (B) photopolymerizable monomer; (C) photopolymerization initiator; (D) colorant; and (E) solvent.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

In Chemical Formula 1 to Chemical Formula 8,

R ¹ is a substituted or unsubstituted C1 to C10 alkyl group,

R ² to R ⁵ and R ⁷ to R ⁹ are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and

R ⁶ is a substituted or unsubstituted C11 to C20 alkyl group.

Based on the total amount of the first acrylic binder resin, the repeating unit represented by Chemical Formula 1 may be included in an amount of 15% by weight to 25% by weight, and the repeating unit represented by Chemical Formula 1 may be included in an amount of 15% by weight to 25% by weight. The repeating unit represented by Chemical Formula 2 may contain the repeating unit represented by Chemical Formula 3 in an amount of 10% by weight to 20% by weight, and may contain the repeating unit represented by Chemical Formula 4 in an amount of 40% by weight to 50% by weight .

Based on the total amount of the second acrylic binder resin, the repeating unit represented by Chemical Formula 1 may be included in an amount of 15% by weight to 25% by weight, and the repeating unit represented by Chemical Formula 1 may be included in an amount of 5% by weight to 15% by weight. The repeating unit represented by Chemical Formula 5 may contain the repeating unit represented by Chemical Formula 6 in an amount of 15% by weight to 25% by weight, and the repeating unit represented by Chemical Formula 7 may be contained in an amount of 35% by weight to 45% by weight, And the repeating unit represented by Chemical Formula 8 may be included in an amount of 5 wt % to 15 wt %.

The weight average molecular weight of the first acrylic binder resin may be 2,000 grams/mole (g/mol) to 9,000 grams/mole (g/mol).

The acid value of the first acrylic binder resin may be 100 mgKOH/g (mgKOH/g) to 120 mgKOH/g (mgKOH/g).

The weight average molecular weight of the second acrylic binder resin may be 10,000 g/mol to 17,000 g/mol.

The acid value of the second acrylic binder resin may be 80 mgKOH/g to 99 mgKOH/g.

The first acrylic binder resin may be included in an amount smaller than the second acrylic binder resin.

The photosensitive resin composition may further include (A3) epoxy binder resin.

The photopolymerizable monomer may include a compound represented by Chemical Formula 9.

[chemical formula 9]

In Chemical Formula 9,

R ¹⁰ to R ¹⁵ are independently represented by Chemical Formula 10,

[chemical formula 10]

Wherein, in chemical formula 10,

n is an integer of 1 or 2.

n can be an integer of 2.

The colorant may include a pigment and a dye represented by Chemical Formula 11.

[chemical formula 11]

In Chemical Formula 11,

Y ¹ to Y ¹² are independently Cl or Br,

R ¹⁶ to R ¹⁹ are independently halogen atoms, substituted or unsubstituted C1 to C20 alkyl, substituted C3 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C6 to C20 aryloxy, and

At least one of R ¹⁶ to R ¹⁹ is represented by Chemical Formula 12,

[chemical formula 12]

Wherein, in chemical formula 12,

R ²⁰ and R ²¹ are independently unsubstituted or C1 to C5 alkyl substituted C1 to C10 alkyl,

o and p are independently integers ranging from 0 to 5, and 1≤o+p≤5.

The dye represented by Chemical Formula 11 may be represented by one selected from Chemical Formula 11-1 to Chemical Formula 11-8.

[Chemical formula 11-1]

[chemical formula 11-2]

[chemical formula 11-3]

[chemical formula 11-4]

[chemical formula 11-5]

[chemical formula 11-6]

[chemical formula 11-7]

[chemical formula 11-8]

The pigments may include green pigments and yellow pigments.

The photopolymerization initiator may include a compound represented by Chemical Formula 13.

[chemical formula 13]

In Chemical Formula 13,

R ²² and R ²³ are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.

Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may include 1% to 10% by weight of the (A1) acrylic binder resin; 5% to 15% by weight of The (A2) acrylic binder resin; 1% to 10% by weight of the (B) photopolymerizable monomer; 0.1% to 5% by weight of the (C) photopolymerization initiator; 30 % by weight to 55% by weight of said (D) colorant; and the balance being said (E) solvent.

The photosensitive resin composition may further include the following additives: malonic acid (malonic acid), 3-amino-1,2-propanediol (3-amino-1,2-propanediol), silane-based coupling agent (silane-based coupling agent), leveling agent (leveling agent), fluorine-based surfactant (fluorine-based surfactant), radical polymerization initiator (radical polymerization initiator) or a combination thereof.

Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

Yet another embodiment provides a color filter including a photosensitive resin layer.

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

The photosensitive resin composition according to the embodiment may improve heat resistance, brightness, surface wrinkle, developing water spots, and thus may be applied to a color filter.

Description of drawings

1 and 2 are photographs showing patterns of photosensitive resin layers manufactured using the photosensitive resin composition according to Example 1, respectively.

3 and 4 are photographs showing patterns of photosensitive resin layers manufactured using the photosensitive resin composition according to Example 2, respectively.

5 and 6 are photographs showing patterns of photosensitive resin layers manufactured using the photosensitive resin composition according to Example 3, respectively.

7 and 8 are photographs showing patterns of photosensitive resin layers manufactured using the photosensitive resin composition according to Example 4, respectively.

9 and 10 are photographs showing patterns of photosensitive resin layers produced using the photosensitive resin composition according to Comparative Example 1, respectively.

11 and 12 are photographs showing patterns of photosensitive resin layers produced using the photosensitive resin composition according to Comparative Example 2, respectively.

13 and 14 are photographs showing patterns of photosensitive resin layers produced using the photosensitive resin composition according to Comparative Example 3, respectively.

15 is a photograph showing a tapered shape and angle of a photosensitive resin layer manufactured using the photosensitive resin composition according to Example 1. FIG.

16 is a photograph showing the tapered shape and angle of a photosensitive resin layer manufactured using the photosensitive resin composition according to Example 2. FIG.

17 is a photograph showing the tapered shape and angle of a photosensitive resin layer manufactured using the photosensitive resin composition according to Example 3. FIG.

18 is a photograph showing the tapered shape and angle of a photosensitive resin layer manufactured using the photosensitive resin composition according to Example 4. FIG.

19 is a photograph showing the tapered shape and angle of a photosensitive resin layer produced using the photosensitive resin composition according to Comparative Example 1. FIG.

20 is a photograph showing the tapered shape and angle of a photosensitive resin layer produced using the photosensitive resin composition according to Comparative Example 2. FIG.

21 is a photograph showing the tapered shape and angle of a photosensitive resin layer manufactured using the photosensitive resin composition according to Comparative Example 3. FIG.

Detailed ways

Hereinafter, examples of the present invention will be described in detail. However, these embodiments are exemplary, and the invention is not limited thereto but only by the scope of the claims.

When no specific definition is otherwise provided, "substituted" as described herein means that at least one hydrogen of the functional group of the present invention is replaced by one or more substituents selected from the group consisting of halogen atoms (F, Cl, Br or I ), hydroxyl, nitro, cyano, amino (NH ₂ , NH(R ²⁰⁰ ) and N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different, and are independently C1 to C10 alkyl), amidino, hydrazino, hydrazone, carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted Or an unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

When no specific definition is provided otherwise, "alkyl" as described herein refers to C1 to C20 alkyl and specifically to C1 to C15 alkyl, and "cycloalkyl" refers to C3 to C20 cycloalkyl and specifically Said C3 to C18 cycloalkyl, "alkoxy" means C1 to C20 alkoxy and specifically C1 to C18 alkoxy, "aryl" means C6 to C20 aryl and specifically C6 to C18 aryl, "alkenyl" means C2 to C20 alkenyl and specifically C2 to C18 alkenyl, "alkylene" means C1 to C20 alkylene and specifically C1 to C18 alkylene Alkyl, and "arylene" refers to a C6 to C20 arylene group and specifically a C6 to C16 arylene group.

When no specific definition is provided otherwise, the "hetero" mentioned herein refers to the inclusion of at least one heteroatom selected from N, O, S and P in the chemical formula.

When no specific definition is otherwise provided, "(meth)acrylate" as used herein refers to both "acrylate" and "methacrylate", and "(meth)acrylic" refers to "acrylic" and "Methacrylate".

As used herein, when a definition is not otherwise provided, when a chemical bond is not drawn where it should be given in a chemical formula, the hydrogen bond is at that position.

When no specific definition is otherwise provided, "*" as used herein indicates a point of attachment to the same or different atoms or chemical formulas.

A photosensitive resin composition according to an embodiment includes: (A1) a first acrylic binder resin including a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and A repeating unit represented by Chemical Formula 4; (A2) a second acrylic binder resin comprising a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 5, a repeating unit represented by Chemical Formula 6, a repeating unit represented by Chemical Formula 7 A repeating unit and a repeating unit represented by Chemical Formula 8; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; and (E) a solvent.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

In Chemical Formula 1 to Chemical Formula 8,

R ¹ is a substituted or unsubstituted C1 to C10 alkyl group,

R ² to R ⁵ and R ⁷ to R ⁹ are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and

R ⁶ is a substituted or unsubstituted C11 to C20 alkyl group.

In general, the color characteristics (eg, brightness, etc.) and pattern characteristics (eg, pattern wrinkles, water stains, etc.) of the color filter can be improved by improving the pigments in the photosensitive resin composition. However, when a pigment is improved, it may not be possible to apply the conventional process to the pigment, and even if applied, the conventional process has little effect on improving color characteristics.

On the contrary, the acrylic binder resin in the photosensitive resin composition according to the embodiment includes repeating units represented by Chemical Formula 1 to Chemical Formula 8, and thus can ensure high heat resistance, pattern surface characteristics, high brightness characteristics, and close contact and control the developability of patterns, and in addition, the acrylic binder resin includes a photopolymerizable monomer represented by a specific chemical formula, a photopolymerization initiator, and a dye, and thus can further effectively improve the above-mentioned characteristics.

Hereinafter, each component is specifically explained.

(A) Acrylic binder resin

The photosensitive resin composition according to the embodiment includes a first acrylic binder resin (A1) including a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, The repeating unit represented by Chemical Formula 3 and the repeating unit represented by Chemical Formula 4.

For example, in chemical formula 1 to chemical formula 4,

R ¹ to R ⁴ may be independently a C1 to C5 alkyl group, R ⁵ may be a hydrogen atom, and R ⁶ may be a substituted or unsubstituted C11 to C18 alkyl group.

In addition, the photosensitive resin composition according to the embodiment includes the second acrylic binder resin (A2) including the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 5, unit, a repeating unit represented by Chemical Formula 6, a repeating unit represented by Chemical Formula 7, and a repeating unit represented by Chemical Formula 8.

For example, in chemical formula 5 to chemical formula 8,

R ¹ to R ⁴ may independently be a C 1 to C 5 alkyl group, and R ⁷ to R ⁹ may independently be a hydrogen atom.

Since the photosensitive resin composition according to the embodiment contains the first acrylic binder resin, the first acrylic binder resin can enhance heat resistance and thus improve brightness, and further, since the photosensitive resin composition Since the second acrylic binder resin is also contained in the resin, the formation of surface wrinkles can be controlled, and the brightness can be further improved.

Based on the total amount of the first acrylic binder resin, the repeating unit represented by Chemical Formula 1 may be included in an amount of 15% by weight to 25% by weight, and the repeating unit represented by Chemical Formula 1 may be included in an amount of 15% by weight to 25% by weight. The repeating unit represented by Chemical Formula 2 may contain the repeating unit represented by Chemical Formula 3 in an amount of 10% by weight to 20% by weight, and may contain the repeating unit represented by Chemical Formula 4 in an amount of 40% by weight to 50% by weight .

Specifically, when the repeating unit represented by Chemical Formula 2 is included in an amount of less than 15% by weight or more than 25% by weight based on the total amount of the first acrylic binder resin, the surface characteristics may be deteriorated, and in terms of brightness improvement, There are limitations.

The first acrylic binder resin may be included in an amount of 1 wt % to 10 wt %, for example, 1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition. In addition, the second acrylic binder resin may be included in an amount of 5% by weight to 15% by weight, for example, 5% by weight to 10% by weight, based on the total amount of the photosensitive resin composition. When the first acrylic binder resin and the second acrylic binder resin are contained within the range, since the crosslinking is improved during the manufacture of the color filter, brightness, heat resistance and developability are improved. Improved and surface smoothness can be enhanced.

In addition, the repeating unit represented by Chemical Formula 1 may be included in an amount of 15 to 25% by weight, and may be included in an amount of 5 to 15% by weight based on the total amount of the second acrylic binder resin. The repeating unit represented by Chemical Formula 5 may contain the repeating unit represented by Chemical Formula 6 in an amount of 15% by weight to 25% by weight, and the repeating unit represented by Chemical Formula 7 may be contained in an amount of 35% by weight to 45% by weight. unit, and the repeating unit represented by Chemical Formula 8 may be included in an amount of 5% by weight to 15% by weight.

When the repeating units represented by Chemical Formula 1 to Chemical Formula 8 included in the first acrylic binder resin and the second acrylic binder resin are within the range, pattern surface characteristics may be further improved.

The first acrylic binder resin may have a weight average molecular weight of 2,000 g/mol to 9,000 g/mol and an acid value thereof of 100 mgKOH/g to 120 mgKOH/g. In addition, the weight average molecular weight of the second acrylic binder resin may be 10,000 g/mol to 17,000 g/mol, and an acid value thereof may be 80 mgKOH/g to 99 mgKOH/g.

When the weight average molecular weight and acid value of the first acrylic binder resin and the second acrylic binder resin are respectively within the ranges, developability during pattern formation and close contact force of patterns may be improved.

The first acrylic binder resin may be included in an amount smaller than the second acrylic binder resin. When the first acrylic adhesive resin is included in the same amount as the second acrylic adhesive resin (or the first acrylic adhesive resin is included in a larger amount than the second acrylic adhesive resin) , developability may deteriorate.

The photosensitive resin composition may further include an epoxy binder resin (A3).

The photosensitive resin composition according to the embodiment may improve heat resistance by further including an epoxy binder resin. The epoxy binder resin may be, for example, phenol novolae epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol Bisphenol F epoxy resin, alicyclic epoxy resin or a combination thereof, but not limited thereto.

In addition, the epoxy binder resin can ensure the dispersion stability of dyes and pigments which will be described later, and at the same time contribute to the formation of pixels with a desired resolution during development.

The epoxy equivalent (g/eq) of the epoxy binder resin may be 150 g/eq to 200 g/eq. When the epoxy binder resin having an epoxy equivalent within the range is included in the binder resin, the epoxy binder resin may increase the degree of curing of the pattern and promote the adhesion of the dye in the patterned structure.

The epoxy binder resin may be included in an amount of 0.1 wt % to 5 wt %, for example, 0.1 wt % to 3 wt %, based on the total amount of the photosensitive resin composition.

(B) Photopolymerizable monomer

The photopolymerizable monomer may be a (meth)acrylate monofunctional or polyfunctional ester containing at least one ethylenically unsaturated double bond, and may be combined with a monofunctional or polyfunctional ester.

The photopolymerizable monomer has an ethylenically unsaturated double bond, and thus, can cause sufficient polymerization during exposure during pattern formation and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ) 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 Acrylates, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol mono Methyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, novolak epoxy (meth)acrylate, or combinations thereof.

Commercially available examples of photopolymerizable monomers are as follows. Monofunctional (meth)acrylates may include Alones (Toagosei Chemistry Industry Co., Ltd.); Kayarad (Nippon Kayaku Co., Ltd.); (Osaka Organic Chemical Ind., Ltd.), etc. Examples of difunctional (meth)acrylates may include Alones (East Asia Chemical Co., Ltd.), Kayarad (Nippon Kayaku Co., Ltd.), (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth)acrylates may include Alones (East Asia Chemical Co., Ltd.), Kayarad (Nippon Kayaku Co., Ltd.), (Osaka Organic Chemical Co., Ltd.), etc. These photopolymerizable monomers may be used alone or in admixture of two or more.

Photopolymerizable monomers can be treated with anhydrides to improve developability.

In addition, the photopolymerizable monomer may further include a compound represented by Chemical Formula 9 in addition to the monofunctional or polyfunctional ester.

[chemical formula 9]

In Chemical Formula 9,

R ¹⁰ to R ¹⁵ are independently represented by Chemical Formula 10,

[chemical formula 10]

Wherein, in chemical formula 10,

n is an integer of 1 or 2.

For example, n can be an integer of 2.

In general, photosensitive resin compositions for color filters mainly contain dipentaerythritol hexaacrylate as a photopolymerizable monomer, but when coated, exposed, developed and cured (post-baked) to form photosensitive When the resin layer is removed, water stains may be generated on the pattern of the photosensitive resin layer, and no solution to definitely solve the water stain problem has been proposed so far.

However, the photosensitive resin composition according to the embodiment includes the compound represented by Chemical Formula 9 as a photopolymerizable monomer, and thus can surely solve the water spot problem.

The photopolymerizable monomer may be included in an amount of 1 wt % to 10 wt %, for example, 5 wt % to 10 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the range, the photopolymerizable monomer is sufficiently cured during exposure in a pattern forming process with excellent reliability, and developability of an alkaline developer may be improved.

(C) Photopolymerization initiator

The photopolymerization initiator can be acetophenone-based compound, benzophenone-based compound, thioxanthone-based compound, benzoin-based compound ), triazine-based compounds, oxime-based compounds, etc.

Examples of acetophenone-based compounds can be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (Methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. .

Examples of benzophenone-based compounds may be benzophenone, benzoylbenzoic acid, benzoylbenzoic acidmethyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminodiphenyl Methanone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

Examples of thioxanthone-based compounds may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone, etc.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Examples of triazine compounds may be 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(trichloro Methyl)-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-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-( 4-methoxystyryl)-s-triazine, etc.

Examples of oxime compounds can be O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-( O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino- 1-phenylpropan-1-one, etc. Specific examples of O-acyl oxime compounds can be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butan-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthio Phenyl)-oct-1,2-diketo-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate, 1 -(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, etc.

For example, the photopolymerization initiator may include an oxime-based compound represented by Chemical Formula 13.

[chemical formula 13]

In Chemical Formula 13,

R ²² and R ²³ are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.

When the photopolymerization initiator of the photosensitive resin composition according to the embodiment includes the compound represented by Chemical Formula 13, close contact force may be improved.

The photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, fluorene-based compounds, and the like in addition to the compounds.

The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and being excited, and then transmitting its energy.

Examples of photosensitizers may be tetraethylene glycolbis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, Mercaptopropionate (dipentaerythritoltetrakis-3-mercaptopropionate), etc.

The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt %, for example, 0.1 wt % to 3 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the range, sufficient photopolymerization occurs during exposure in a pattern forming process, and deterioration of transmittance due to the non-reactive initiator can be prevented.

(D) Colorant

The photosensitive resin composition according to the embodiment includes a colorant, and the colorant may include a pigment, a dye, or a combination thereof. For example, the colorant may include a pigment and a dye represented by Chemical Formula 11.

[chemical formula 11]

In Chemical Formula 11,

Y ¹ to Y ¹² are independently Cl or Br,

R ¹⁶ to R ¹⁹ are independently halogen atoms, substituted or unsubstituted C1 to C20 alkyl, substituted C3 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl or substituted or unsubstituted C6 to C20 aryloxy, and

At least one of R ¹⁶ to R ¹⁹ is represented by Chemical Formula 12,

[chemical formula 12]

Wherein, in chemical formula 12,

R ²⁰ and R ²¹ are independently unsubstituted or C1 to C5 alkyl substituted C1 to C10 alkyl,

o and p are independently integers ranging from 0 to 5, and 1≤o+p≤5.

The compound represented by Chemical Formula 11 has improved green spectral characteristics and high brightness. In addition, the compound represented by Chemical Formula 11 contains an aryloxy group represented by Chemical Formula 12, the aryloxy group contains an alkyl group as a substituent, and since the alkyl group is unsubstituted or substituted only with an alkyl group, the compound Can have excellent solubility in organic solvents.

R ²⁰ and R ²¹ above may independently be a substituent comprising isopropyl or tert-butyl (eg tert-butyl) at the terminus. The alkyl group (substituent of the aryloxy group represented by Chemical Formula 12) includes isopropyl group or tert-butyl group (eg, tert-butyl group), and thus may increase solubility in an organic solvent and achieve excellent brightness.

o and p are independently an integer of 1. The aryloxy group represented by Chemical Formula 12 contains two substituted or unsubstituted alkyl groups as alkyl substituents, and thus can have better solubility in an organic solvent than the aryloxy group containing one alkyl group as a substituent .

For example, Chemical Formula 12 may be represented by Chemical Formula 12-1.

[Chemical formula 12-1]

In Chemical Formula 12-1,

R ²⁰ and R ²¹ are independently substituted or unsubstituted C1 to C10 alkyl as the alkyl group.

R ²⁰ may exist in an ortho position with respect to the oxygen atom of the aryloxy group, and R ²¹ may exist in a para position with respect to the oxygen atom of the aryloxy group. When the alkyl substituent is present at each of the ortho and para positions relative to the oxygen atom of the aryloxy group, superiority in solubility and brightness can be obtained compared to when the alkyl substituent does not exist at the above positions Effect.

For example, at least two (eg, at least three) of R ¹⁶ to R ¹⁹ may be represented by Chemical Formula 12. For example, all R ¹⁶ to R ¹⁹ may be represented by Chemical Formula 12.

The greater the number of substituents represented by Chemical Formula 12, the better the solubility in an organic solvent that the compound according to one embodiment has.

The dye represented by Chemical Formula 11 may be represented by one selected from Chemical Formula 11-1 to Chemical Formula 11-8.

[Chemical formula 11-1]

[chemical formula 11-2]

[chemical formula 11-3]

[chemical formula 11-4]

[chemical formula 11-5]

[chemical formula 11-6]

[chemical formula 11-7]

[chemical formula 11-8]

Pigments may include organic pigments such as red pigments, green pigments, blue pigments, yellow pigments, and the like. For example, the pigment can be a green pigment, a yellow pigment, or a combination thereof.

Examples of the red pigment may be color index (C.I.) red pigment 254, C.I. red pigment 255, C.I. red pigment 264, C.I. red pigment 270, C.I. red pigment 272, C.I. red pigment 177, C.I. red pigment 89, and the like.

Examples of green pigments may be halogen-substituted copper phthalocyanine pigments, such as C.I. Green Pigment 58, C.I. Green Pigment 59, C.I. Green Pigment 36, C.I. Green Pigment 7, and the like.

Examples of blue pigments may be ketophthalocyanine pigments such as C.I. Blue Pigment 15:6, C.I. Blue Pigment 15, C.I. Blue Pigment 15:1, C.I. Blue Pigment 15:2, C.I. Blue Pigment 15:3 , C.I. Blue Pigment 15:4, C.I. Blue Pigment 15:5, C.I. Blue Pigment 16, etc.

Examples of yellow pigments can be isoindoline-based pigments (isoindoline-based pigments), such as C.I. Yellow Pigment 139; quinophthalone-based pigments (quinophthalone-based pigments), such as C.I. Yellow Pigment 138; complex pigment), such as C.I. Yellow Pigment 150, etc.

The pigments may be used alone or in admixture of two or more, but are not limited thereto.

The photosensitive resin composition may further include a dispersant to improve the dispersibility of the pigment. Specifically, the photosensitive resin composition may be prepared by pretreating the surface of the pigment with a dispersant or adding the pigment together with the dispersant.

The dispersant may be a nonionic dispersant, anionic dispersant, cationic dispersant, or the like. Specific examples of the dispersant may be polyalkylene glycol and its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonate, carboxylate , carboxylate, alkylamide alkylene oxide addition product, alkylamine, etc., and these dispersants may be used alone or as a mixture of two or more.

Commercially available examples of the dispersant may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161 manufactured by BYK Co., Ltd. , DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001; EFKA Chemicals .) made of EFKA (EFKA)-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450; Zeneka Co. Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or PB711, etc. manufactured by Ajinomoto Inc.

The dispersant may be included in an amount of 0.1% by weight to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the range, the composition has excellent stability, developability, and pattern-forming ability due to improved dispersion properties during manufacture of a light blocking layer.

Pigments can be pretreated with water-soluble inorganic salts and wetting agents. When the pigment is pretreated, the average particle size of the pigment can become finer.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the kneaded pigment.

The kneading may be performed at a temperature of 40° C. to 100° C., and filtering and washing may be performed by filtering the pigment after washing away the inorganic salt with water or the like.

Examples of water-soluble inorganic salts may be sodium chloride, potassium chloride, etc., but are not limited thereto. The wetting agent can uniformly mix and pulverize the pigment and the water-soluble inorganic salt. Examples of wetting agents include alkyleneglycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.; alcohols such as ethanol, isopropanol , butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, etc. These wetting agents may be used alone or in admixture of two or more.

The kneaded pigment may have an average particle diameter ranging from 30 nanometers (nm) to 100 nanometers (nm). When the average particle diameter of the pigment is within the range, heat resistance and light resistance are improved, and fine patterns can be efficiently formed.

Specifically, the pigment may be used in the form of a pigment dispersion liquid containing a dispersant and a solvent which will be described later, and the pigment dispersion liquid may contain a solid pigment, a dispersant, and a solvent. The solid pigment may be contained in an amount of 10% by weight to 15% by weight based on the total amount of the pigment dispersion liquid.

The colorant may be included in an amount of 30% by weight to 55% by weight, for example, 30% by weight to 50% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included within the range, brightness, color reproducibility, pattern curability, heat resistance, and close contact force are improved.

(E) solvent

The solvent is a material that is compatible with, but does not react with, the binder resin, photopolymerizable monomer, photopolymerization initiator, and colorant.

Examples of solvents may include alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol methyl ether, ethyl ether, etc. Glycol ethyl ether, propylene glycol methyl ether, etc.; cellosolve acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; card Alcohols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.; ketones, such as Methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, etc.; Saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactate, such as methyl lactate, ethyl lactate, etc.; alkyl glycolate, such as glycolic acid Methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxy Alkyl methyl ester, ethoxyethyl acetate, etc.; Alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; Alkyl 3-alkoxypropionate Esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; Alkyl esters, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate , ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionate, such as 2-hydroxy - Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionate, such as 2-methoxy-2-methylpropionate methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyacetate ethyl ester, methyl 2-hydroxy-3-methylbutyrate, etc.; or ketoesters, such as ethyl pyruvate, etc., and additionally N-methylformamide, N,N-dimethylformamide, N -Methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isofor Alone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma-butyrolactone , ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., and these solvents may be used alone or in admixture of two or more.

In consideration of miscibility and reactivity, glycol ethers, such as ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetate, such as ethyl cellosolve, can be advantageously used Ethyl cellosolve acetate, etc.; esters, such as 2-hydroxyethyl propionate (2-hydroxyethyl propionate), etc.; diethylene glycol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkanes propylene glycol alkylether acetate, such as propylene glycol monomethylether acetate, propylene glycol propylether acetate, etc.

Based on the total amount of the photosensitive resin composition, the solvent may be included in a balance (for example, 30% by weight to 60% by weight, for example, 30% by weight to 50% by weight). When the solvent is included within the range, coating properties of the photosensitive resin composition are improved, and a film with improved flatness can be obtained.

(F) Other additives

The photosensitive resin composition may further contain the following other additives to prevent stains or spots during coating, to adjust leveling, or to prevent pattern residue due to undeveloped: for example, malonic acid; 3-amino-1,2- Propylene glycol; a silane coupling agent; a leveling agent; a fluorosurfactant; a radical polymerization initiator; or a combination thereof.

Examples of silane-based coupling agents can be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., and these silane coupling agents can be used alone or as a mixture of two or more.

Examples of the fluorosurfactant may be the following commercially available fluorosurfactants: e.g. and (BM Chemie Inc.); MEGAFACE F f f and F (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FULORAD FULORAD and FULORAD (Sumitomo 3M Co., Ltd.); SURFLON SURFLON SURFLON SURFLON and SURFLON (Asahi Glass Co., Ltd.); and and etc. (Toray Silicone Co., Ltd.).

The amounts of these additives can be adjusted according to the desired properties.

Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

Yet another embodiment provides a color filter including the photosensitive resin layer.

The method of manufacturing the color filter is as follows.

The above photosensitive resin composition is coated on a glass substrate by an appropriate method (eg, spin coating, roll coating, spray coating, etc.) to form a resin composition layer with a thickness of 0.5 μm to 10 μm.

Subsequently, the substrate having the resin composition layer is irradiated with light to form a pattern required for the color filter. Irradiation can be performed using ultraviolet rays, electron beams, or X-rays as a light source, and ultraviolet rays can be irradiated, for example, in a region of 190 nm to 450 nm, specifically, 200 nm to 400 nm. Irradiation may be performed by further using a photoresist mask. After performing the irradiation process in this way, the resin composition layer exposed to the light source is treated with a developer. Herein, the unexposed area in the resin composition layer dissolves and forms a pattern for the color filter. This process can be repeated several times depending on the number of colors required to obtain a color filter with a desired pattern. In addition, when the image pattern obtained by development in the above process is cured by reheating or irradiating actinic rays thereto, crack resistance, solvent resistance, and the like can be improved.

Hereinafter, the present invention is explained in more detail with reference to Examples. However, these examples should not be construed as limiting the scope of the invention in any sense.

(Preparation of Acrylic Binder Resin)

Synthesis Example 1 to Synthesis Example 4

2 g of AIBN as an initiator was put into a 100 ml beaker, to which monomers for polymerization were sequentially added at the ratios shown in Table 1 until the total was 40 g, and the mixture was stirred for 30 minutes. Subsequently, 70 g of propylene glycol monomethyl ether acetate was put into a 250 ml glass reactor equipped with a cooler to perform a polymerization reaction, and then heated to 85° C., and the prepared monomer solution was added dropwise thereto over 3 hours . After the reaction was further performed at the same temperature for 6 hours and then the temperature was lowered to room temperature, the reaction was completed, and herein, the reaction was performed under a nitrogen atmosphere.

(Table 1)

(unit weight%)

polymerizable monomer Synthesis Example 1 Synthesis example 2 Synthesis example 3 Synthesis Example 4 Methacrylate 20 20 20 20 Isobornyl Acrylate 20 - 10 30 N-phenylmaleimide 15 - 25 5 lauryl acrylate 45 - 45 45 Methyl methacrylate - 10 - - Cyclohexyl methacrylate - 20 - - Cyclohexylmaleimide - 40 - - Tricyclodecanyl Methacrylate - 10 - - Weight average molecular weight (Mw, g/mol) 8,500 11,000 8,900 7,600 Acid value (mgKOH/g) 110 90 120 101

(Preparation of Photosensitive Resin Composition)

Example 1 to Example 7 and Comparative Example 1 to Comparative Example 3

The photosensitive resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were prepared to have each composition shown in Table 2 using the following components, respectively.

Specifically, after accurately measuring the content of the photopolymerization initiator, a solvent was added thereto, and the mixture was sufficiently stirred until the photopolymerization initiator was completely dissolved therein (greater than or equal to 30 minutes). Subsequently, an acrylic binder resin, an epoxy binder resin, and a photopolymerizable monomer were sequentially added thereto, and the obtained mixture was further stirred for one hour. Then, a colorant and other additives were sequentially added thereto, and finally the obtained mixture was stirred for more than or equal to 2 hours to prepare photosensitive resin compositions respectively.

Each component used in the photosensitive resin composition is as follows.

(A) Binder resin

(A-1) Acrylic binder resin of Synthesis Example 1

(A-2) Acrylic binder resin of Synthesis Example 2

(A-3) Epoxy adhesive resin (epoxy equivalent: 177g/eq) (EHPE-3150, DAICELCHEMICAL)

(A-4) Acrylic binder resin of Synthesis Example 3

(A-5) Acrylic binder resin of Synthesis Example 4

(A-6) Acrylic adhesive resin (SKY-095, Samsung SDI Co., Ltd.)

(A-7) Acrylic adhesive resin (SKY-141, Samsung SDI Co., Ltd.)

(A-8) Acrylic binder resin (BX-04, Nippon Shokubai Co., Ltd.)

(B) Photopolymerizable monomer

(B-1) KAYARAD DPCA-120 (Nippon Kayaku Co., Ltd.)

(B-2) DPHA (Nippon Kayaku Co., Ltd.)

(B-3) Viscoat 1000 (OSAKA YUKI)

(C) Photopolymerization initiator

(C-1) Oxime-based initiator (NCI-930, ADEKA Corp.)

(C-2) Oxime-based initiator (OXE-02, BASF Corp.)

(D) Colorant

(D-1) Green dye represented by Chemical Formula 11-1

[Chemical formula 11-1]

(D-2) Green pigment dispersion (G58, ENF (ENF))

(D-3) Green Pigment Dispersion (G59, ENF Company)

(D-4) Auxiliary Yellow Pigment Dispersion Liquid (SC-P541-2236 Yellow-M, TOYO Ink LLC.)

(E) solvent

Propylene glycol monomethylether acetate (PGMEA)

(F) Other additives

Fluorinated surfactant (F-554 (10% diluted solution), Dickson Co., Ltd.)

(Table 2)

(unit weight%)

Assessment 1: Color Properties

Utilize coating machine (Obi Carter (Opticoat) MS-A150, Mikasa Co., Ltd. (Mikasa Co., Ltd.)) to be able to obtain the number of revolutions per minute (rpm) of predetermined thickness respectively according to example 1 to example 7 and comparison The photosensitive resin compositions of Examples 1 to Comparative Example 3 were applied, and then prebaked on a 90° C. hot plate. Subsequently, the entire surface of the prebaked composition was respectively subjected to light exposure using an exposure machine (HB-50110AA, Ushio Inc.) at 50 millijoules/square centimeter (mj/cm ² ). exposed, and then baked in an oven at 230° C. for 20 minutes to fabricate samples, respectively. The color characteristics (color coordinates (Gx, Gy), brightness (Y), contrast ratio (contrast ratio, CR)) of the samples before and after baking in the oven were measured by MCPD 3000 equipment, and the results are shown in the table 3 in.

(table 3)

Gx Gy Brightness (Y) Contrast Ratio (CR) Example 1 0.2840 0.649 55.70 12415 Example 2 0.2840 0.649 55.73 12225 Example 3 0.2841 0.649 55.72 12315 Example 4 0.2841 0.649 55.78 12921 Example 5 0.2840 0.649 55.55 12185 Example 6 0.2841 0.649 55.60 12235 Example 7 0.2841 0.649 55.61 12312 Comparative example 1 0.2841 0.649 55.33 12133 Comparative example 2 0.2841 0.649 55.42 12284 Comparative example 3 0.2838 0.649 55.42 12484

Evaluation 2: Pattern wrinkles, water stains, close contact force, and taper

The photosensitive resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were respectively treated with a coater (Opticoat MS-A150, Mikasa Co., Ltd.) at a revolution per minute (rpm) capable of obtaining a predetermined thickness. coated and then dried naturally at room temperature (15°C to 25°C) for 30 minutes. Then, utilize an exposure machine (HB-50110AA, Youzhiwang Company) under the condition of 50mj/cm ² to carry out pattern exposure to the dried photosensitive resin composition respectively with a pattern mask, under the pressure of 1.5kgf Developed in 20-fold diluted Na ₂ CO ₃ as a developer, washed under a pressure of 1.0kgf, and then examined pattern wrinkles, water stains, close contact force, and taper with an optical microscope , and the results are shown in Table 4 and Figures 1 to 21.

Pattern Wrinkle Evaluation Benchmark

○: No pattern wrinkles

x: patterned folds

Patterned Water Spot Evaluation Benchmark

○: No pattern water stains

△: some pattern water stains

x: many patterned water spots

(Table 4)

patterned folds patterned water stains Close contact force (μm) Cone angle (°) Example 1 ○ △ 14 54.14 Example 2 ○ ○ 14 50.25 Example 3 ○ △ 12 61.53 Example 4 ○ ○ 12 48.10 Example 5 △ △ 15 55.44 Example 6 △ △ 15 54.35 Example 7 ○ △ 16 58.12 Comparative example 1 x x 18 - Comparative example 2 x x 18 - Comparative example 3 x x 18 -

Referring to Table 3 and Table 4 and FIGS. 1 to 21 , compared with the photosensitive resin compositions according to Comparative Examples 1 to 3, the photosensitive resin compositions according to Examples 1 to 7 exhibited excellent developability , close contact force, pattern characteristics, tapered characteristics, etc., and excellent color characteristics (such as brightness, etc.). Specifically, when the repeating unit represented by Chemical Formula 2 is included in an amount of 15% by weight to 25% by weight based on the total amount of the first acrylic binder resin, brightness and close contact force are more excellent, and pattern wrinkles are further improved. improve.

While the present invention has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover all aspects contained in the appended claims. Various modifications and equivalent arrangements are within the spirit and scope. Therefore, the above-mentioned embodiments should be understood as exemplary rather than limiting the present invention in any way.

Claims (19)

1. A photosensitive resin composition, characterized in that, comprising A first acrylic binder resin comprising a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4; A second acrylic binder resin comprising a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 5, a repeating unit represented by Chemical Formula 6, a repeating unit represented by Chemical Formula 7, and a repeating unit represented by Chemical Formula 8; photopolymerizable monomers; photopolymerization initiator; colorants; and solvent, [chemical formula 1] [chemical formula 2] [chemical formula 3] [chemical formula 4] [chemical formula 5] [chemical formula 6] [chemical formula 7] [chemical formula 8] Wherein, in chemical formula 1 to chemical formula 8, R ¹ is a substituted or unsubstituted C1 to C10 alkyl group, R ² to R ⁵ and R ⁷ to R 9 are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and R ⁶ is a substituted or unsubstituted C11 to C20 alkyl group. 2. The photosensitive resin composition according to claim 1, characterized in that Based on the total amount of the first acrylic binder resin, The repeating unit represented by Chemical Formula 1 is included in an amount of 15% by weight to 25% by weight, comprising the repeating unit represented by Chemical Formula 2 in an amount of 15% by weight to 25% by weight, The repeating unit represented by Chemical Formula 3 is included in an amount of 10% by weight to 20% by weight, and The repeating unit represented by Chemical Formula 4 is included in an amount of 40% by weight to 50% by weight. 3. The photosensitive resin composition according to claim 1, characterized in that Based on the total amount of the second acrylic binder resin, The repeating unit represented by Chemical Formula 1 is included in an amount of 15% by weight to 25% by weight, comprising the repeating unit represented by Chemical Formula 5 in an amount of 5% by weight to 15% by weight, comprising the repeating unit represented by Chemical Formula 6 in an amount of 15% by weight to 25% by weight, The repeating unit represented by Chemical Formula 7 is included in an amount of 35% by weight to 45% by weight, and The repeating unit represented by Chemical Formula 8 is included in an amount of 5% by weight to 15% by weight. 4 . The photosensitive resin composition according to claim 1 , wherein the weight average molecular weight of the first acrylic binder resin is 2,000 g/mol to 9,000 g/mol. 5 . The photosensitive resin composition according to claim 1 , wherein the acid value of the first acrylic binder resin is 100 mgKOH/g to 120 mgKOH/g. 6 . The photosensitive resin composition according to claim 1 , wherein the weight average molecular weight of the second acrylic binder resin is 10,000 g/mol to 17,000 g/mol. 7 . The photosensitive resin composition according to claim 1 , wherein the acid value of the second acrylic binder resin is 80 mgKOH/g to 99 mgKOH/g. 8 . The photosensitive resin composition according to claim 1 , wherein the amount of the first acrylic binder resin contained is smaller than that of the second acrylic binder resin. 9. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises an epoxy binder resin. 10. The photosensitive resin composition according to claim 1, wherein the photopolymerizable monomer comprises a compound represented by Chemical Formula 9: [chemical formula 9] Wherein, in chemical formula 9, R ¹⁰ to R ¹⁵ are independently represented by Chemical Formula 10, [chemical formula 10] Wherein, in chemical formula 10, n is an integer of 1 or 2. 11 . The photosensitive resin composition according to claim 10 , wherein n is an integer of 2. 12. The photosensitive resin composition according to claim 1, wherein the colorant comprises a pigment and a dye represented by chemical formula 11: [chemical formula 11] Wherein, in chemical formula 11, Y ¹ to Y ¹² are independently Cl or Br, R ¹⁶ to R ¹⁹ are independently halogen atoms, substituted or unsubstituted C1 to C20 alkyl, substituted C3 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl or substituted or unsubstituted C6 to C20 aryloxy, and At least one of R ¹⁶ to R ¹⁹ is represented by Chemical Formula 12, [chemical formula 12] Wherein, in chemical formula 12, R ²⁰ and R ²¹ are independently unsubstituted or C1 to C5 alkyl substituted C1 to C10 alkyl, o and p are independently integers ranging from 0 to 5, and 1≤o+p≤5. 13. The photosensitive resin composition according to claim 12, wherein the dye represented by Chemical Formula 11 is represented by one selected from Chemical Formula 11-1 to Chemical Formula 11-8: [Chemical formula 11-1] [chemical formula 11-2] [chemical formula 11-3] [chemical formula 11-4] [chemical formula 11-5] [chemical formula 11-6] [chemical formula 11-7] [chemical formula 11-8] 14. The photosensitive resin composition according to claim 12, wherein the pigment comprises a green pigment and a yellow pigment. 15. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises a compound represented by Chemical Formula 13: [chemical formula 13] Wherein, in chemical formula 13, R ²² and R ²³ are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ is a substituted or unsubstituted C1 to C10 alkylene group. 16. The photosensitive resin composition according to claim 1, wherein, based on the total amount of the photosensitive resin composition, the photosensitive resin composition comprises: 1% to 10% by weight of said acrylic binder resin; 5% to 15% by weight of said acrylic binder resin; 1% to 10% by weight of said photopolymerizable monomer; 0.1% to 5% by weight of said photopolymerization initiator; 30% to 55% by weight of said colorant; and The balance is the solvent. 17. The photosensitive resin composition according to claim 1, characterized in that, the photosensitive resin composition further comprises the following additives: malonic acid, 3-amino-1,2-propanediol, silane coupling agent, A leveling agent, a fluorosurfactant, a radical polymerization initiator or a combination thereof. 18. A photosensitive resin layer, characterized in that it is manufactured using the photosensitive resin composition according to any one of claims 1 to 17. 19. A color filter, comprising the photosensitive resin layer according to claim 18.