KR20230057533A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition, which contains: (A) a binder resin polymerized from a monomer mixture containing a specific content of a monomer of a specific structure; (B) a photopolymerizable compound; (C) photopolymerization initiator; (D) colorants including xanthene-based dyes and pigments; and (E) a solvent, a photosensitive resin film manufactured using the photosensitive resin composition, and a color filter manufactured using the same. One embodiment is intended to provide improved heat resistance and chemical resistance of a hybrid photosensitive resin composition.

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film and a color filter prepared using the photosensitive resin composition.

A liquid crystal display device, which is one of display devices, has advantages such as light weight, thinness, low cost, low power consumption drive, and excellent bonding with integrated circuits, and its use range is expanding for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, color filter, and ITO pixel electrode are formed, an active circuit unit composed of a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper substrate on which an ITO pixel electrode is formed.

The color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block the boundary between pixels and a plurality of colors (usually red (R), green (G), and blue (B) to form each pixel). ) has a structure in which the three primary colors of ) are arranged in a predetermined order, and the pigment dispersion method, which is one of the methods for realizing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, This is a method in which a colored thin film is formed by repeating a series of processes of exposing a pattern of the shape to be formed, removing the unexposed area with a solvent and curing it with heat. Compositions are generally composed of alkali-soluble resins, photopolymerization monomers, photopolymerization initiators, epoxy resins, solvents, and other additives, etc. The pigment dispersion method having the above characteristics is actively used in manufacturing LCDs such as mobile phones, laptop computers, monitors, and TVs. is being applied

In recent years, in order to overcome the limitations of luminance and contrast ratio caused by the size of pigment particles, research on hybrid photosensitive resin compositions in which non-particle dyes are introduced along with pigments has been continued. However, in the case of a hybrid type photosensitive resin color filter composition, it has weak heat resistance and chemical resistance compared to a pigment type as a disadvantage.

One embodiment is to improve heat resistance and chemical resistance of a hybrid photosensitive resin composition.

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

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

One embodiment of the present invention is (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; and (E) a solvent; wherein the colorants include dyes and pigments; The dye includes a xanthene-based dye; The binder resin is a polymer of a monomer mixture including a monomer represented by Formula 1 below; Provides a photosensitive resin composition containing 5 to 20% by weight of the monomer represented by Formula 1 in the total amount of the monomer mixture:

[Formula 1]

R ¹ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ² is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ³ is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

The monomer mixture may further include a monomer represented by Formula 2 below, a monomer represented by Formula 3 below, a monomer represented by Formula 4 below, a monomer represented by Formula 5 below, or a combination thereof:

[Formula 2]

In Formula 2, R ⁴ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ⁵ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;

[Formula 3]

In Formula 3, R ⁶ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ⁷ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ⁸ is a substituted or unsubstituted alkyl having 1 to 10 carbon atoms;

[Formula 4]

In Formula 4, R ⁹ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ¹⁰ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; L is a single bond or an alkylene having 1 to 10 carbon atoms;

[Formula 5]

In Formula 5, R ¹¹ is hydrogen, alkyl having 1 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms.

Of the total amount of the monomer mixture, the monomer represented by Formula 2 is included in 15 to 40% by weight, the monomer represented by Formula 3 is included in 25 to 60% by weight, and the monomer represented by Formula 4 is included in 0 to 20% by weight. % by weight, and the monomer represented by Formula 5 may be included in an amount of 5 to 30% by weight.

An acid value of the binder resin may be 170 to 270 mgHOK/g.

The weight average molecular weight of the binder resin may be 5000 to 30000 g/mol.

The xanthene-based dye may be a xanthene-based red dye.

The xanthene-based red dye may be a compound represented by Formula 6 below:

[Formula 6]

In Formula 6, R ¹² is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ¹³ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

The pigment includes a blue pigment, and the blue pigment may include a phthalocyanine-based blue pigment.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) binder resin 1% to 20% by weight; 0.1% to 7% by weight of the (B) photopolymerizable monomer; 0.1% to 5% by weight of the (C) photopolymerization initiator; 15% to 55% by weight of the (D) colorant; and (E) the remainder of the solvent.

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; And it may further include at least one additive selected from a radical polymerization initiator.

Another embodiment provides a photosensitive resin film prepared 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 specific details of other aspects of the present invention are included in the detailed description below.

The photosensitive resin composition according to an embodiment is a hybrid type including a pigment along with a xanthene dye, and may have heat resistance and chemical resistance equal to or higher than that of the pigment type.

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 herein, "substitution" means that at least one hydrogen atom in a compound is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, No group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt. , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group , A C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a substituent of a combination thereof.

Unless otherwise specified herein, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" mean cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl, respectively. It means that at least one N, O, S or P heteroatom exists in the ring compound of ene.

Unless otherwise specified herein, "(meth)acrylate" means both "acrylate" and "methacrylate".

Unless otherwise defined herein, "combination" means mixing or copolymerization. Further, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formula within this specification, if 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 to the position.

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

One implementation is

(A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; and (E) a solvent; wherein the colorants include dyes and pigments; The dye includes a xanthene-based dye; The binder resin is a polymer of a monomer mixture including a monomer represented by Formula 1 below; Provides a photosensitive resin composition containing 5 to 20% by weight of the monomer represented by Formula 1 in the total amount of the monomer mixture:

[Formula 1]

R ¹ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ² is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ³ is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

Although the photosensitive resin composition is a hybrid type containing a pigment together with a xanthene-based dye, a binder resin polymerized from a monomer mixture containing a specific content of the monomer represented by Formula 1 is used. Based on this, it may have chemical resistance equal to or higher than that of the pigment type.

Specifically, the binder resin is an acrylic composite binder resin polymerized from a monomer mixture including the monomer represented by Chemical Formula 1.

In particular, the binder resin is an acrylic composite binder resin polymerized from a monomer mixture containing 5 to 20% by weight of the monomer represented by Formula 1. When the content of the monomer represented by Formula 1 in the monomer mixture is 5 to 20% by weight, the hydrophilic interaction of the xanthene-based dye can be remarkably expressed.

As a result, the photosensitive resin film prepared using the photosensitive resin composition of one embodiment can suppress elution of the xanthene-based dye and exhibit chemical resistance equal to or higher than that of the pigment type.

Hereinafter, each component included in the photosensitive resin composition will be described in detail.

(A) binder resin

The binder resin may include a monomer represented by Chemical Formula 1; And an acrylic composite binder resin polymerized from a monomer mixture including at least one monomer having a structure different therefrom.

For example, the monomer represented by Chemical Formula 1 may be 2-(hydroxyethyl)methacrylate. In this case, all of R ¹ are hydrogen; wherein R ² is hydrogen or methyl; R ³ is ethylene, and 5 to 20% by weight of the monomer represented by Formula 1 is included in the total amount of the monomer mixture. When these ranges are satisfied, excellent heat resistance and chemical resistance of the photosensitive resin composition and the photosensitive resin film including the same can be contributed.

The monomer mixture may further include a monomer represented by Formula 2 below. The high acid value of the binder resin is attributed to the monomer represented by the formula (2). Specifically, the monomer represented by Chemical Formula 1 has a high acid value (eg, 170 mgHOK/g or more) based on the *-(C=O)-OH structure.

In this case, the binder resin may further include a second structural unit derived from a monomer represented by Formula 2 below:

[Formula 2]

In Formula 2, R ⁴ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ⁵ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

For example, the monomer represented by Chemical Formula 2 may be acrylate or methacrylate. In this case, all of R ⁴ are hydrogen; The R ⁵ may be hydrogen or methyl.

Of the total amount of the monomer mixture, the monomer represented by Formula 2 may be included in 15 to 40% by weight. Specifically, of the total amount of the monomer mixture, the monomer represented by Formula 2 is 15% by weight or more, 18% by weight or more, 20% by weight or more, or 22% by weight or more, and 40% by weight, 35% by weight, or 30% by weight %, 27% or 25% by weight or less. When these ranges are satisfied, the photosensitive resin composition including the xanthene-based ionic dye can secure excellent chemical resistance.

The monomer mixture may further include a monomer represented by Formula 3 below. In this case, the binder resin may further include a third structural unit derived from a monomer represented by Formula 3 below, and may have excellent processability due to the third structural unit.

[Formula 3]

In Formula 3, R ⁶ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ⁷ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ⁸ is a substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

For example, the monomer represented by Chemical Formula 3 may be methyl acrylate or methyl methacrylate. In this case, all of R ⁶ are hydrogen; wherein R ⁷ is hydrogen or methyl; The R ⁸ may be methyl.

Of the total amount of the monomer mixture, the monomer represented by Formula 3 may be included in 25 to 60% by weight. Specifically, of the total amount of the monomer mixture, the monomer represented by Formula 3 is 25% by weight or more, 27% by weight or more, 30% by weight or more, or 35% by weight or more, and 60% by weight, 55% by weight, or 53% by weight %, or up to 50% by weight. When these ranges are satisfied, the photosensitive resin composition may have excellent processability.

The monomer mixture may further include a monomer represented by Chemical Formula 4 below. In this case, the binder resin may further include a fourth structural unit derived from a monomer represented by Formula 4 below, and adhesion may be improved by the fourth structural unit:

[Formula 4]

In Formula 4, R ⁹ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ¹⁰ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; L is a single bond or an alkylene having 1 to 10 carbon atoms;

For example, the monomer represented by Chemical Formula 4 may be dicyclopentanyl acrylate or dicyclopentanyl methacrylate. In this case, all of R ⁹ are hydrogen; The R ¹⁰ may be hydrogen or methyl.

Of the total amount of the monomer mixture, the monomer represented by Chemical Formula 4 may be included in an amount of 0 to 20% by weight. Specifically, the monomer mixture represented by Chemical Formula 4 may not be included (0 wt%), but may be included in more than 0 wt% of the total amount of the monomer mixture. More specifically, of the total amount of the monomer mixture, the monomer represented by Formula 4 is greater than 0% by weight, 2% by weight or more, 4% by weight or more, or 6% by weight or more, and 20% by weight, 17% by weight, 13% by weight % by weight, or up to 10% by weight. When these ranges are satisfied, the photosensitive resin composition may have excellent adhesion.

The monomer mixture may further include a monomer represented by Formula 5 below. In this case, the binder resin may further include a fifth structural unit derived from a monomer represented by Formula 5 below, and heat resistance may be improved by the fifth structural unit:

[Formula 5]

In Formula 5, R ¹¹ is hydrogen, alkyl having 1 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms.

For example, the monomer represented by Chemical Formula 5 may be phenyl maleimide. In this case, the R ¹⁰ may be phenyl.

Of the total amount of the monomer mixture, the monomer represented by Chemical Formula 5 may be included in an amount of 5 to 30% by weight. Specifically, of the total amount of the monomer mixture, the monomer represented by Formula 5 is 5% by weight or more, 8% by weight or more, 10% by weight or more, or 12% by weight or more, and 30% by weight, 25% by weight, or 20% by weight %, or up to 18% by weight. When these ranges are satisfied, the photosensitive resin composition may have excellent heat resistance.

The acid value of the binder resin may be 170 to 270 mgHOK/g. When the acid value of the binder resin is within the above range, excellent compatibility with the xanthene-based dye having hydrophilicity may be expressed. As a result, the photosensitive resin film prepared using the photosensitive resin composition of one embodiment can suppress elution of the xanthene-based dye and exhibit heat resistance and chemical resistance equal to or higher than those of the pigment type.

The weight average molecular weight of the binder resin may be 5000 to 30000 g/mol. When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to a substrate when manufacturing a color filter.

The binder resin may further include an acrylic resin.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and includes one or more acrylic repeating units.

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

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

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, or vinylbenzylmethyl ether; 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 resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate late copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and the like, but are not limited thereto, and may be used alone or in combination of two or more. .

The binder resin may further include an epoxy-based binder resin.

The binder resin may improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin may include, for example, a phenol novolak epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an alicyclic epoxy resin, or a combination thereof, but is limited thereto It is not.

Furthermore, the binder resin including the epoxy-based binder resin secures dispersion stability of a colorant such as a pigment, which will be described later, and helps to form a pixel having a desired resolution during a developing process.

The epoxy-based binder resin 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 binder resin. When the epoxy-based binder resin is included in the above range, film remaining rate and chemical resistance may be greatly improved.

The epoxy equivalent weight of the epoxy-based binder resin may be 150 g/eq to 200 g/eq. When an epoxy-based binder resin having an epoxy equivalent within the above range is included in the binder resin, there is an advantageous effect in improving the curing degree of the formed pattern and fixing the colorant in the patterned structure.

The binder resin may be dissolved in a solvent to be described later in a solid form to form a photosensitive resin composition. In this case, the binder resin in the solid form may be about 10% to 50% by weight, for example, 20% to 40% by weight based on the total amount of the binder resin solution dissolved in the solvent.

The binder resin may be included in an amount of 1 wt % to 20 wt %, for example, 3 wt % to 15 wt %, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, it is possible to obtain excellent surface smoothness due to excellent developability and improved crosslinking property during manufacture of the color filter.

(B) photopolymerizable compound

The photopolymerizable compound may be a monofunctional or multifunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

The photopolymerizable compound has the ethylenically unsaturated double bond, so that it can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate Latex, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate ) acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

Examples of commercially available products of photopolymerizable compounds are as follows. Examples of monofunctional esters of (meth)acrylic acid include Aronix M- ^101® , M- ^111® , and M- ^114® from Toagosei Chemical Industry Co., Ltd.; KAYARAD TC-110S ^® of Nippon Kayaku Co., Ltd., the same TC-120S ^® , etc.; Osaka Yuki Kagaku Kogyo Co., Ltd.'s V- ^158® , V- ^2311® , etc. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid include Aronix M- ^210® , M- ^240® , and M- ^6200® of Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA ^® from Nippon Kayaku Co., Ltd., HX-220 ^® , R-604 ^® , etc.; Examples include V- ^260® , V- ^312® , and V-335 ^HP® of Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronix M- ^309® , M- ^400® , M- ^405® , M- ^450® , and M from Toagosei Chemical Industry Co., Ltd. -710 ^® , copper M-8030 ^® , copper M-8060 ^® , etc.; KAYARAD TMPTA ^® from Nippon Kayaku Co., Ltd., Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® , etc.; V-295 ^® , Dong-300 ^® , Dong-360 ® , Dong-GPT ^® , Dong-3PA ^® , Dong-400 ^® and ^the like of Osaka Yuki Kayaku Kogyo Co., Ltd. These products may be used alone or in combination of two or more.

The photopolymerizable compound may be used after being treated with an acid anhydride to impart better developability.

The photopolymerizable compound may be included in an amount of 0.1 wt % to 7 wt %, for example, 0.1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability and excellent developability with an alkaline developer.

(C) photopolymerization initiator

The photopolymerization initiator is an initiator generally used in photosensitive resin compositions, 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, p-t-butyltrichloro acetophenone, p-t -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(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-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

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, and the like.

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 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-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O- Acetate etc. are mentioned.

As the photopolymerization initiator, a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, a fluorene-based compound, and the like may be used in addition to the above compounds.

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

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like. can be heard

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 above range, excellent reliability can be obtained due to sufficient curing during exposure in the pattern forming process, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to the unreacted initiator A decrease in transmittance can be prevented.

(D) colorant

The colorants include dyes and pigments; The dye includes a xanthene-based dye.

As mentioned above, since the xanthene-based dye has strong hydrophilicity, it is possible to interact with the first structural unit having a high acid value in the binder resin. As a result, the photosensitive resin film prepared using the photosensitive resin composition of one embodiment can suppress elution of the xanthene dye and exhibit heat resistance and chemical resistance equal to or higher than those of the pigment type.

The xanthene-based dye is a material that exhibits fluorescence of yellow to pink, blue, and bright colors. Specifically, the xanthene-based dye is a xanthene-based red dye and may be represented by Formula 6 below:

[Formula 6]

In Formula 6, R ¹² is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms; R ¹³ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms. For example, all of R ¹² may be ethyl, and all of R ¹³ may be ethyl.

The pigment includes a blue pigment, and the blue pigment may include a phthalocyanine-based blue pigment. The phthalocyanine-based pigment covers a range from bright blue to green and is known as a material having excellent color intensity and chemical stability.

The phthalocyanine-based pigment is a phthalocyanine-based blue pigment, and the pigments of the same color index (C.I.) number such as C.I Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, respectively Two or more types may be used in combination.

The colorant may be used together with a dispersant to form a composition. Specifically, the pigment may be used after surface treatment with a dispersant in advance, or a dispersant may be added together with the pigment during preparation of the composition.

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

For example, commercially available products of the dispersant include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK from BYK. -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 and the like from EFKA Chemical; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711, PB821, etc.

The dispersing agent 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 in preparing a color filter are excellent according to the excellent dispersibility of the composition.

The pigment may be used after pretreatment with a water-soluble inorganic salt and a wetting agent. When the pigment is used after being pretreated, 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, but are not limited to, sodium chloride and potassium chloride. The wetting agent serves as a medium in which the pigment and the water-soluble inorganic salt are uniformly mixed and the pigment can be easily pulverized, examples of which include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether. alkylene glycol monoalkyl ethers; and 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, for example, 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, stability in the pigment dispersion is excellent, and there is no fear of deterioration in pixel resolution.

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 as the solvent forming the pigment dispersion.

Specifically, the pigment may be used in the form of a pigment dispersion containing 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 wt % to 20 wt %, for example, 8 wt % to 15 wt %, based on the total amount of the pigment dispersion.

The colorant may be included in an amount of 15 wt % to 55 wt %, for example, 20 wt % to 50 wt %, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the coloring effect and developability are excellent.

(E) solvent

As the solvent, materials that have compatibility with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator but 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; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetic acid alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as 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 methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 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, 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as methyl ethyl propionate; esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; ketonic acid esters such as ethyl pyruvate, etc., and also N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid and high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, considering compatibility and reactivity, ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as 2-hydroxy ethyl propionate; carbitols such as diethylene glycol monomethyl ether; Propylene glycol 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 amount, for example, 30 wt% to 70 wt%, for example, 35 wt% to 65 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, it is possible to obtain a coating film having excellent coatability of the photosensitive resin composition and excellent flatness.

(F) other additives

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; Surfactants; And it may further include at least one additive selected from a radical polymerization initiator.

The additives can be easily adjusted according to desired physical properties.

The coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ Isocyanate propyl triethoxysilane, (gamma) glycidoxy propyl trimethoxysilane, (beta) epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The silane-based coupling agent may be specifically used in an amount of 0.01 part 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 color filters may further include a surfactant, such as a fluorine-based surfactant, if necessary.

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

The surfactant is preferably included in an amount of 0.01% to 5% by weight and more preferably in an amount of 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 to cause a problem in that foreign substances 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 prepared using the photosensitive resin composition according to the embodiment is provided.

According to another embodiment, a color filter manufactured using the photosensitive resin composition described above is provided.

A manufacturing method of the color filter is as follows.

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

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 range 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 irradiation step in this way, the photosensitive resin composition layer irradiated with the light source is treated with a developing solution. At this time, the unexposed portion of the photosensitive resin composition layer is dissolved to form a pattern required for the color filter. By repeating this process according to the number of colors required, 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, etc., crack resistance, solvent resistance, and the like can be improved.

According to another embodiment, a display device including the above is provided. The "display" device may be, for example, a liquid crystal display (LCD).

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 binder resin)

Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 10

In a 200 ml beaker, 50 g of polymerization monomers were sequentially added at the weight % ratios specified in Tables 1 to 3 below. Then, 3.5 g of V601 (wako) as an initiator, 0.1 g of mercaptoethanol (TCI) as a chain transfer agent, and 37.5 g of PGMEA (dicel) as a solvent were added, followed by stirring for 60 minutes to prepare a monomer solution.

To proceed with the polymerization reaction, 86.7 g of PGMEA was added to a 250 ml glass reactor equipped with a cooler, the temperature was raised to 85 ° C, and 92 g of the prepared monomer solution was dropped into the reactor at a constant rate for 3 hours. After the reaction was further progressed at the same temperature for 8 hours, the temperature was lowered to room temperature and the reaction was terminated. The reaction was conducted under a nitrogen atmosphere.

The acid value of each binder resin obtained as a result was measured by the following process. A mixed solvent containing toluene, isopropyl alcohol, and distilled water at a weight ratio of 50:49.5:0.5 was prepared. Next, about 0.5 g (based on solid content) of the binder resin was precisely weighed and dissolved in 50 g of the mixed solvent. In this way, a sample solution for titration was prepared. This sample solution was subjected to neutralization titration with a KOH aqueous solution of 0.1 N using a titrator, type "COMTITE-550" manufactured by HIRANUMA. The acid value of the binder resin was calculated by the obtained result and the following formula (1).

[Equation 1]

Acid value [mgKOH/g] = (a-b) × 5.611 × F/S

In Equation 2,

a: Amount of KOH aqueous solution required for titration of the sample solution [ml]

b: Amount of KOH aqueous solution required for titration of the blank (mixed solvent) [ml]

F: Titer of KOH aqueous solution

S: Weight of resin contained in the sample solution used for titration [g]

In addition, the weight average molecular weight (Mw) of each binder resin was measured by gel permeation chromatography (GPC: PL GPC220, Agilent Technologies) under the following conditions.

- Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column are used in combination

- Solvent: 2% by weight of amine compound mixed with tetrahydrofuran

- Flow rate: 1.0ml/min

- Sample concentration: 0.1wt%

- Injection amount: 37.5ml

- column temperature: 40 ° C

- Detector: RI detector 35℃

- Standard: Polystyrene (correction with cubic function)

monomer type Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 unit Glycidyl methacrylate - - - - - - weight% 4-hydroxybutyl acrylate - - - - - - weight% Acrylic acid 26 26 26 16 26 26 weight% methacrylic acid - 10 weight% Ethylhexyl methacrylate - - - - - - weight% methyl methacrylate 46 46 39 46 49 44 weight% Hydroxyethyl methacryalte 5 13 20 13 10 15 weight% dicyclopentanyl methacrylate 8 - - - - - weight% Phenyl maleimdie 15 15 15 15 15 15 weight% Acid value 202 202 202 190 202 202 mgKOH/g Molecular Weight (Mw) 11,600 11,900 12,400 11,500 11,600 11,600 g/mol

monomer type comparison
Synthesis Example 1 comparison
Synthesis Example 2 comparison
Synthesis Example 3 comparison
Synthesis Example 4 comparison
Synthesis Example 5 unit Glycidyl methacrylate - - - - - weight% 4-hydroxybutyl acrylate - - - - - weight% Acrylic acid 22 24 26 28 26 weight% methacrylic acid - weight% Ethylhexyl methacrylate - - - - - weight% methyl methacrylate 46 46 46 46 32 weight% Hydroxyethyl methacryalte - - - - 27 weight% dicyclopentanyl methacrylate 17 15 13 11 - weight% Phenyl maleimdie 15 15 15 15 15 weight% Acid value (mgKOH/g) 171 186 202 218 202 mgKOH/g Molecular Weight (Mw, g/mol) 11,400 12,000 11,500 11,500 11,300 g/mol

monomer type comparison
Synthesis Example 6 comparison
Synthesis Example 7 comparison
Synthesis Example 8 comparison
Synthesis Example 9 unit Glycidyl methacrylate - - - - weight% 4-hydroxybutyl acrylate - - - - weight% Acrylic acid 26 18 26 26 weight% methacrylic acid weight% Ethylhexyl methacrylate 46 - - - weight% methyl methacrylate - 46 56 36 weight% Hydroxyethyl methacryalte - - 3 23 weight% dicyclopentanyl methacrylate 13 21 - - weight% Phenyl maleimdie 15 15 15 15 weight% Acid value (mgKOH/g) 202 140 202 202 mgKOH/g Molecular Weight (Mw, g/mol) 11,400 11,900 11,600 11,600 g/mol

(Synthesis of photosensitive resin composition)

Examples 1 to 6 and Comparative Examples 1 to 10

A photosensitive resin composition was prepared by mixing the compositions shown in Tables 4 to 6.

Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 30 minutes, and then a binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 60 minutes. Subsequently, a dye and a pigment dispersion as a colorant were added to the obtained reactant and stirred at room temperature for 30 minutes. Subsequently, a photosensitive resin composition was prepared by filtering the product twice to remove impurities.

(Unit: % by weight) ingredient material name solid content
(%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) binder resin A-1 100 1.0 1.0 1.0 1.0 1.0 1.0 A-2 45 2.2 2.2 2.2 2.2 2.2 2.2 A-3 30 10.0 - - - - - A-4 30 - 10.0 - - - - A-5 30 - - 10.0 - - - A-6 30 - - - 10.0 - - A-7 30 - - - - 10.0 A-8 30 - - - - - 10.0 (B) photopolymerizable compound B-1 100 1.2 1.2 1.2 1.2 1.2 1.2 B-2 100 3.7 3.7 3.7 3.7 3.7 3.7 (C) photopolymerization initiator C-1 100 1.1 1.1 1.1 1.1 1.1 1.1 C-2 100 0.4 0.4 0.4 0.4 0.4 0.4 (D) colorant D-1 17 19.8 19.8 19.8 19.8 19.8 19.8 D-2 10 2.7 2.7 2.7 2.7 2.7 2.7 (E) solvent E-1 - 57.6 57.6 57.6 57.6 57.6 57.6 (F) additives F-1 10 0.3 0.3 0.3 0.3 0.3 0.3

(Unit: % by weight) ingredient material name solid content
(%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) binder resin A-1 100 1.0 1.0 1.0 1.0 1.0 A-2 45 2.2 2.2 2.2 2.2 2.2 A-9 30 10.0 - - - - A-10 30 - 10.0 - - - A-11 30 - - 10.0 - - A-12 30 - - - 10.0 - A-13 30 - - - - 10.0 (B) photopolymerizable compound B-1 100 1.2 1.2 1.2 1.2 1.2 B-2 100 3.7 3.7 3.7 3.7 3.7 (C) photopolymerization initiator C-1 100 1.1 1.1 1.1 1.1 1.1 C-2 100 0.4 0.4 0.4 0.4 0.4 (D) colorant D-1 17 19.8 19.8 19.8 19.8 19.8 D-2 10 2.7 2.7 2.7 2.7 2.7 (E) solvent E-1 - 57.6 57.6 57.6 57.6 57.6 (F) additives F-1 10 0.3 0.3 0.3 0.3 0.3

(Unit: % by weight) ingredient material name solid content
(%) Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 (A) binder resin A-1 100 1.0 1.0 1.0 1.0 1.0 1.0 A-2 45 2.2 2.2 2.2 2.2 2.2 2.2 A-3 30 - - - - - 10.0 A-14 30 10.0 - - - - - A-15 30 - 10.0 - - - - A-16 30 - - 10.0 - - - A-17 30 - - - 10.0 - - A-18 30 - - - - 10.0 - (B) photopolymerizable compound B-1 100 1.2 1.2 1.2 1.2 1.2 1.2 B-2 100 3.7 3.7 3.7 3.7 3.7 3.7 (C) photopolymerization initiator C-1 100 1.1 1.1 1.1 1.1 1.1 1.1 C-2 100 0.4 0.4 0.4 0.4 0.4 0.4 (D) colorant D-1 17 19.8 19.8 19.8 19.8 19.8 19.8 D-2 10 2.7 2.7 2.7 2.7 2.7 - D-3 10 - - - - - 2.7 (E) solvent E-1 - 57.6 57.6 57.6 57.6 57.6 57.6 (F) additives F-1 10 0.3 0.3 0.3 0.3 0.3 0.3

(A) binder resin

(A-1) Epoxy-based binder resin (product name: EHPE3150, manufacturer: Dicel)

(A-2) cardo-based binder resin (product name: KBR-101, manufacturer: Kyeongin Corporation)

(A-3) Acrylic Composite Binder Resin (Synthesis Example 1)

(A-4) Acrylic Composite Binder Resin (Synthesis Example 2)

(A-5) Acrylic Composite Binder Resin (Synthesis Example 3)

(A-6) Acrylic Composite Binder Resin (Synthesis Example 4)

(A-7) Acrylic Composite Binder Resin (Synthesis Example 5)

(A-8) Acrylic Composite Binder Resin (Synthesis Example 6)

(A-9) Acrylic Composite Binder Resin (Comparative Synthesis Example 1)

(A-10) Acrylic Composite Binder Resin (Comparative Synthesis Example 2)

(A-11) Acrylic Composite Binder Resin (Comparative Synthesis Example 3)

(A-12) Acrylic Composite Binder Resin (Comparative Synthesis Example 4)

(A-13) Acrylic Composite Binder Resin (Comparative Synthesis Example 5)

(A-14) Acrylic Composite Binder Resin (Comparative Synthesis Example 6)

(A-15) Acrylic Composite Binder Resin (Comparative Synthesis Example 7)

(A-16) Acrylic binder resin (product name: NPR5216, manufacturer: Miwon)

(A-17) Acrylic Composite Binder Resin (Comparative Synthesis Example 8)

(A-18) Acrylic Composite Binder Resin (Comparative Synthesis Example 9)

(B) photopolymerizable compound

(B-1) photopolymerizable monomer (substance name: dipentaerythritol hexaacrylate (DPHA), manufacturer: Nippon Explosive)

(B-2) Caprolactone-modified multifunctional acrylate (product name: DPCA120, manufacturer: Nippon Explosives)

(C) photopolymerization initiator

(C-1) SPI-03W (Manufacturer: Samyang Corporation)

(C-2) DFI020 (Manufacturer: KISCO)

(D) colorant

(D-1) phthalocyanine-based pigment dispersion (product name: B15:6, manufacturer: Sanyo)

(B-2) xanthone red dye dispersion (product name: Acid red 52, manufacturer: TCI)

(B-3) Non-xanthone red dye dispersion (product name: Nile Red (Cas no: 7385-67-3), manufacturer: Sigma-Aldrich)

(E) solvent

Propylene glycol monomethyl ether acetate (PGMEA, manufacturer: Sigma-Aldrich)

(F) additives

Fluorinated surfactant (F-554, manufacturer: DIC)

(evaluation)

Each resin film was prepared using the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5, and heat resistance and chemical resistance were evaluated.

Evaluation 1: heat resistance

The color filter composition prepared in Table 2 was applied to a thickness of 2.3 μm to 2.5 μm on a degreased and washed glass substrate having a thickness of 1 mm, and dried on a hot plate at 90 ° C. for 2 minutes to obtain a coating film. Subsequently, the whole surface was exposed to the coating film under conditions of 40 mJ/cm ² using a UV lamp having a dominant wavelength of 365 nm. Thereafter, samples were obtained by drying in a hot air oven at 230° C. for 20 minutes.

The prepared sample was dried in a hot air oven at 240 ° C. for 1 hour, and the color value before and after the forging was measured using MCPD (Otsuka Co.) equipment.

The heat resistance was analyzed by calculating the ΔEab* value, which is a measure of color change, according to Equation 2 below, and the results are shown in Table 7 below.

[Equation 1]

ΔEab* = {(ΔL*) ² + (Δa*) ² + (Δb*) ² } x 1/2

For reference, it can be seen that the smaller the ΔEab* value calculated from Equation 2, the better the heat resistance and chemical resistance of the resin film.

heat resistance
(240℃, 1hr) NMP chemical resistance
(room temperature, 10min) ΔEab* ΔEab* Example 1 1.6 2.2 Example 2 1.8 1.9 Example 3 1.9 1.6 Example 4 1.5 1.8 Example 5 1.9 2.0 Example 6 1.7 1.6 Comparative Example 1 1.7 4.0 Comparative Example 2 1.7 3.8 Comparative Example 3 1.6 3.6 Comparative Example 4 1.7 3.3 Comparative Example 5 1.9 3.0 Comparative Example 6 2.5 4.5 Comparative Example 7 2.2 7.5 Comparative Example 8 1.9 6.8 Comparative Example 9 1.7 2.8 Comparative Example 10 1.9 2.7 Comparative Example 11 2.5 8.0

From Table 7, it can be seen that the photosensitive resin composition according to one embodiment has excellent heat resistance and chemical resistance compared to the photosensitive resin compositions of Comparative Examples 1 to 11.

Furthermore, by comparing Examples 1 to 6, it can be seen that heat resistance and chemical resistance can be controlled by appropriately adjusting the compounding ratio of components constituting the photosensitive resin composition.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims and detailed description of the invention and the accompanying drawings, and this also It goes without saying that it falls within the scope of the invention.

Claims (14)

(A) a binder resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a colorant; and
(E) solvent
including,
The colorants include dyes and pigments;
The dye includes a xanthene-based dye;
The binder resin is a polymer of a monomer mixture including a monomer represented by Formula 1 below;
A photosensitive resin composition comprising 5 to 20% by weight of the monomer represented by Formula 1 in the total amount of the monomer mixture:
[Formula 1]

R ¹ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ² is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ³ is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.
According to claim 1,
The monomer mixture further comprises a monomer represented by Chemical Formula 2, a monomer represented by Chemical Formula 3, a monomer represented by Chemical Formula 4, a monomer represented by Chemical Formula 5, or a combination thereof:
[Formula 2]

In Formula 2,
R ⁴ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ⁵ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
[Formula 3]

In Formula 3,
R ⁶ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ⁷ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ⁸ is a substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
[Formula 4]

In Formula 4,
R ⁹ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ¹⁰ is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
L is a single bond or an alkylene having 1 to 10 carbon atoms;
[Formula 5]

In Formula 5,
R ¹¹ is hydrogen, alkyl of 1 to 10 carbon atoms, or aryl of 6 to 10 carbon atoms.
According to claim 2,
Of the total amount of the monomer mixture, the monomer represented by Formula 2 is included in 15 to 40% by weight, the monomer represented by Formula 3 is included in 25 to 60% by weight, and the monomer represented by Formula 4 is included in 0 to 20% by weight. A photosensitive resin composition comprising 5 to 30% by weight of the monomer represented by Formula 5.
According to claim 1,
The acid value of the binder resin is 170 to 270 mgHOK / g of the photosensitive resin composition.
According to claim 1,
The weight average molecular weight of the binder resin is 5000 to 30000 g / mol of the photosensitive resin composition.
According to claim 1,
The xanthene-based dye is a xanthene-based red dye photosensitive resin composition.
According to claim 6,
The photosensitive resin composition wherein the xanthene-based red dye is a compound represented by Formula 6:
[Formula 6]

In Formula 6,
R ¹² , identical or different, is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms;
R ¹³ is the same or different, and is hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

According to claim 1,
The photosensitive resin composition comprising a blue pigment.
According to claim 8,
The blue pigment is a photosensitive resin composition comprising a phthalocyanine-based blue pigment.
According to claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
1% to 20% by weight of the (A) binder resin;
0.1% to 7% by weight of the (B) photopolymerizable monomer;
0.1% to 5% by weight of the (C) photopolymerization initiator;
15% to 55% by weight of the (D) colorant; and
The remaining amount of the above (E) solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; And a photosensitive resin composition further comprising at least one additive selected from a radical polymerization initiator.
A photosensitive resin film prepared using the photosensitive resin composition of claim 1.
A color filter comprising the photosensitive resin film of claim 12 .
A display device comprising the color filter of claim 13.