KR20230050529A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition, a photosensitive resin film manufactured using the photosensitive resin composition, and a color filter including the same. The photosensitive resin composition comprises: (A) a binder resin dispersion; (B) a photopolymerization compound; (C) a photopolymerization initiator; (D) a colorant dispersion; and (E) a solvent. The binder resin dispersion includes a binder resin and a first dispersion medium, wherein the binder resin contains a specific structural unit. The colorant dispersion includes a dye dispersion and a pigment dispersion, wherein the dye dispersion contains a phthalocyanine-based dye and a second dispersion medium. In addition, a content relationship between the phthalocyanine-based dye and the specific structural unit is controlled. Accordingly, heat resistance and chemical resistance of a hybrid photosensitive resin composition are improved.

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 dispersion; (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant dispersion; and (E) a solvent, wherein the binder resin dispersion includes a binder resin and a first dispersion medium; The binder resin includes a first structural unit derived from a monomer represented by Formula 1 below; the colorant dispersion includes a dye dispersion and a pigment dispersion; The dye dispersion includes a phthalocyanine-based dye and a second dispersion medium; Provided is a photosensitive resin composition comprising 15 to 65 parts by weight of the first structural unit based on 100 parts by weight of the phthalocyanine dye:

[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 11 to 20 substituted or unsubstituted alkyl.

Of the total amount of the binder resin dispersion, the binder resin may be included in 20 to 40% by weight.

Of the total amount of the dye dispersion, the phthalocyanine-based dye may be included in an amount of 1 to 15% by weight.

Of the total amount of the binder resin, the first structural unit may be included in 15 to 50% by weight.

The binder resin may include a second structural unit derived from a monomer represented by Formula 2 below, a third structural unit derived from a monomer represented by Formula 3 below, a fourth structural unit derived from a monomer represented by Formula 4 below, or It may further include combinations of these:

[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; L is a single bond or an alkylene having 1 to 10 carbon atoms;

[Formula 4]

In Formula 4, R ⁸ is hydrogen, alkyl having 1 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms.

Of the total amount of the binder resin, the second structural unit may be included in 5 to 30% by weight, the third structural unit may be included in 15 to 60% by weight, and the fourth structural unit may be included in 5 to 30% by weight.

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

The phthalocyanine-based dye may be represented by Formula 5 below:

[Formula 5]

In Formula 5, R ⁹ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group. group or a substituted or unsubstituted C6 to C20 aryloxy group; However, at least one of R ⁹ to R ²⁴ is represented by the following formula (6);

[Formula 6]

In Formula 6, R ²⁵ and R ²⁶ are each independently a halogen atom, an alkyl having 1 to 10 carbon atoms, or a branched chain alkyl having 4 to 10 carbon atoms; n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≤ n1 + n2 ≤ 5.

The pigment dispersion may include a green pigment dispersion, a yellow pigment dispersion, or a combination thereof.

the green pigment dispersion includes a green pigment and a third dispersion medium; Of the total amount of the green pigment dispersion, the green pigment may be included in 10 to 30% by weight.

the yellow pigment dispersion includes a yellow pigment and a fourth dispersion medium; Of the total amount of the yellow pigment dispersion, the yellow pigment may be included in 10 to 30% by weight.

Of the total amount of the colorant dispersion, 0.1 to 10% by weight of the green pigment dispersion, 10 to 25% by weight of the yellow pigment dispersion, and the balance of the phthalocyanine-based dye dispersion may be included.

The photosensitive resin composition may include, based on the total amount of the photosensitive resin composition, 1% to 15% by weight of the (A) binder resin dispersion; 0.1% to 10% by weight of the (B) photopolymerizable compound; 0.1% to 5% by weight of the (C) photopolymerization initiator; and 15% to 55% by weight of the (D) colorant dispersion; 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 and 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 one embodiment is a hybrid type including a pigment along with a phthalocyanine-based 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 embodiment is A) a binder resin dispersion; (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant dispersion; and (E) a solvent, wherein the binder resin dispersion includes a binder resin and a first dispersion medium; The binder resin includes a first structural unit derived from a monomer represented by Formula 1 below; the colorant dispersion includes a dye dispersion and a pigment dispersion; The dye dispersion includes a phthalocyanine-based dye and a second dispersion medium; Provided is a photosensitive resin composition comprising 15 to 65 parts by weight of the first structural unit based on 100 parts by weight of the phthalocyanine dye:

[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 11 to 20 substituted or unsubstituted alkyl.

Although the photosensitive resin composition is a hybrid type including a pigment along with a phthalocyanine-based dye, a binder resin containing the first structural unit is used and the first structural unit is used in relation to the content of the phthalocyanine-based dye. Based on the fact that the content of is controlled to a specific range, etc., it may have heat resistance and chemical resistance equal to or higher than that of the pigment type.

Specifically, the binder resin is an acrylic composite binder resin including the first structural unit, and has strong hydrophobicity as it includes an alkyl having a long chain length (ie, R ³ = 11 to 20 substituted or unsubstituted alkyl). can have Since the phthalocyanine-based dye also has hydrophobicity, it is possible to interact with R ³ , which is a strong hydrophobic group in the binder resin. In particular, the first structural unit in the binder resin is included in an amount of 15 to 65 parts by weight, specifically 15 to 50 parts by weight, based on 100 parts by weight of the phthalocyanine dye. As a result, the photosensitive resin film prepared using the photosensitive resin composition of one embodiment can suppress elution of the phthalocyanine-based dye and exhibit heat resistance and chemical resistance equal to or higher than those of the pigment type.

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

(A) binder resin dispersion

As mentioned above, the binder resin dispersion includes a binder resin and a first dispersion medium. In addition, the binder resin is an acrylic composite binder resin, and the binder resin includes a first structural unit derived from a monomer represented by Formula 1 below.

The first structural unit is derived from an ester-based monomer having a high molecular weight compared to the second structural unit described below.

Specifically, the first structural unit is an acid containing substituted or unsubstituted alkyl having 1 to 10 carbon atoms or substituted or unsubstituted alkenyl having 2 to 10 carbon atoms; and alcohols including long-chain alkyls (ie, R ³ = 11 to 20 substituted or unsubstituted alkyls).

For example, in the first structural unit, all of R ¹ are hydrogen; R ² is hydrogen or methyl; R ³ may be 12 or 18. Here, the first structural unit in which R ³ is 12 may be derived from lauryl (meth)acrylate, and the first structural unit in which R ³ is 18 may be derived from stearyl (meth)acrylate.

However, the first structural unit is not particularly limited as long as it is derived from the monomer represented by Formula 1.

Of the total amount of the binder resin, the first structural unit may be included in 15 to 50% by weight. Specifically, of the total amount of the binder resin, the first structural unit is 15% by weight or more, 20% by weight or more, 21% by weight or more, 22% by weight or more, 23% by weight or more, 24% by weight or more, or 25% by weight or more. In addition, it may be 50% by weight or less, 49% by weight or less, 48% by weight or less, 47% by weight or less, or 45% by weight or less. When these ranges are satisfied, the photosensitive resin composition can secure excellent heat resistance and chemical resistance.

Meanwhile, the binder resin includes a second structural unit derived from a monomer represented by Formula 2 below, a third structural unit derived from a monomer represented by Formula 3 below, and a fourth structural unit derived from a monomer represented by Formula 4 below. , or may further include 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;

L is a single bond or an alkylene having 1 to 10 carbon atoms;

[Formula 4]

In Formula 4,

R ⁸ is hydrogen, alkyl of 1 to 10 carbon atoms, or aryl of 6 to 10 carbon atoms.

The second structural unit is derived from a monomer having a low molecular weight and an acid value compared to the first structural unit, and having an 'acid value' here means having a 'carboxy group'.

For example, all of R ⁴ are hydrogen; The R ⁵ may be hydrogen or methyl. Here, the second structural unit in which R ⁵ is hydrogen may be derived from acrylate, and the second structural unit in which R ⁵ is methyl may be derived from methacrylate.

Of the total amount of the binder resin, the second structural unit may be included in an amount of 5 to 30% by weight. Specifically, of the total amount of the binder resin, the second structural unit is 5% by weight or more, 7% by weight or more, 9% by weight or more, 11% by weight or more, or 12% by weight or more, and 30% by weight or less, 25% by weight or less , 20 wt% or less, 18 wt% or less, 15 wt% or less, or 12 wt% or less. When these ranges are satisfied, the photosensitive resin composition can secure excellent processability.

On the other hand, the monomer represented by Chemical Formula 3 has an effect of enhancing the strength and adhesion of the photosensitive resin film due to its rigid ring structure, and the monomer represented by Chemical Formula 4 has a high glass transition temperature to heat resistance of the photosensitive resin film. has a strengthening effect.

The monomer represented by Chemical Formula 3 may be tricyclodecanyl methacrylate (TCDMA) represented by Chemical Formula 3-1.

[Formula 3-1]

In Formula 4, R ⁷ is hydrogen, alkyl having 1 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms. For example, R ⁷ is phenyl, and the monomer represented by Chemical Formula 4 may be phenyl maleimide represented by Chemical Formula 4-1 below.

[Formula 4-1]

Of the total amount of the binder resin, 15 to 60% by weight of the third structural unit may be included, and 5 to 30% by weight of the fourth structural unit may be included. Specifically, of the total amount of the binder resin, the monomer represented by Formula 3 is 15% by weight or more, 20% by weight or more, 22% by weight or more, 24% by weight or more, 26% by weight or more, or 28% by weight or more, and 60 55 wt% or less, 50 wt% or less, or 48 wt% or less. In addition, of the total amount of the binder resin, the monomer represented by Chemical Formula 4 is 5% by weight or more, 7% by weight or more, 9% by weight or more, 11% by weight or more, or 13% by weight or more, and 30% by weight or less, 25% by weight or more % or less, 20% or less, or 18% or less.

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 is in the form of a solid component, and constitutes the photosensitive resin composition in the form of a binder dispersion using a solvent described later as a first dispersion medium. The binder resin in the solid form may be about 20 to 40% by weight, for example, 25 to 35% by weight based on the total amount of the binder resin dispersion dissolved in the first dispersion medium.

The binder resin dispersion may be included in an amount of 1 to 15% by weight, specifically 1 to 10% by weight, for example, 3 to 10% by weight, 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 ^® , M-8030 ^® , 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 10 wt%, 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 dispersion

the colorant dispersion includes a dye dispersion and a pigment dispersion; The dye dispersion includes a phthalocyanine-based dye and a second dispersion medium.

As mentioned above, since the phthalocyanine-based dye also has hydrophobicity, it is possible to interact with R ³ , which is a strong hydrophobic group 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 phthalocyanine-based dye and exhibit heat resistance and chemical resistance equal to or higher than those of the pigment type.

The phthalocyanine-based dye may be represented by Formula 5 below:

[Formula 5]

In Formula 5, R ⁹ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group. group or a substituted or unsubstituted C6 to C20 aryloxy group; However, at least one of R ⁹ to R ²⁴ is represented by the following formula (6);

[Formula 6]

In Formula 6, R ²⁵ and R ²⁶ are each independently a halogen atom, an alkyl having 1 to 10 carbon atoms, or a branched chain alkyl having 4 to 10 carbon atoms; n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≤ n1 + n2 ≤ 5.

Specifically, the substituent represented by Formula 6 may be a substituent represented by any one of Formulas 6-1 to 6-4 below.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

In Formulas 6-1 to 6-3, R ²⁷ is the same or different halogen atom;

[Formula 6-4]

In Formula 6-4, R ²⁸ is alkyl having 1 to 10 carbon atoms; R ²⁹ is branched-chain alkyl of 4 to 10 carbon atoms.

Since the phthalocyanine-based dye includes a substituent represented by any one of Formulas 6-1 to 6-4, it is possible to express more vivid colors even with a small amount, and when used as a colorant, excellent color characteristics such as luminance and contrast ratio Manufacture of display elements is possible. For example, the phthalocyanine-based dye may be a colorant, for example, a dye, for example, a green dye, for example, a dye having maximum transmittance in a wavelength range of 445 nm to 560 nm. In addition, the green dye may be a dye having maximum absorbance in a wavelength range of 600 nm to 730 nm.

That is, since the green dye has maximum transmittance in the wavelength range of 445 nm to 560 nm and maximum absorbance in the wavelength range of 600 nm to 730 nm, when the green dye is used as a colorant together with the green pigment dispersion and the yellow pigment dispersion , it is possible to improve the coloring power, luminance and contrast ratio by implementing much higher color coordinates.

For example, the phthalocyanine-based dye may be represented by any one of Chemical Formulas 5-1 to 5-11.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

Of the total amount of the dye dispersion, the phthalocyanine-based dye may be included in an amount of 1 to 15% by weight, for example, 1 to 10% by weight. When configured within the above content range, a colorant having excellent coloring power may be implemented, and a color filter having excellent luminance and contrast ratio may be implemented by using the colorant.

As the second dispersion medium, a nonionic dispersion medium, an anionic dispersion medium, or a cationic dispersion medium may be used. Specific examples of the dispersion medium 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 second dispersion medium are BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165 , DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450 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 second dispersion medium 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 dispersion medium is included within the above range, stability, developability, and patternability when preparing a color filter are excellent according to the excellent dispersibility of the composition.

The pigment dispersion may include a green pigment dispersion, a yellow pigment dispersion, or a combination thereof.

Each of the above pigments may be used after being pretreated using 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.

Specifically, the green pigment dispersion includes a green pigment and a third dispersion medium; Of the total amount of the green pigment dispersion, the green pigment may be included in an amount of 10 to 30% by weight, for example, 15 to 25% by weight. In addition, the yellow pigment dispersion includes a yellow pigment and a fourth dispersion medium; Of the total amount of the yellow pigment dispersion, the yellow pigment may be included in an amount of 10 to 30% by weight, for example, 15 to 25% by weight.

Ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. may be used as the third or fourth dispersion medium forming the pigment dispersion.

The colorant dispersion 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 phthalocyanine-based dyes)

Dye Synthesis Example 1

1) 3,4,5,6-tetrachlorophthalonitrile (5g), 2-tert-Butyl-4-methylphenol (3.09g), K2CO3 (3.9g), N,N-dimethylformamide (N,N- dimethylformamide) (25ml) was added and stirred while heating to 70°C. After completion of the reaction, extract with EA (ethyl acetate). After extraction and concentration, it is purified by column chromatography. After purification, vacuum drying is performed to obtain 4-(2-tert-Butyl-4-methyl phenoxy)-3,5,6-trichloro-phthalonitrile.

2) 4-(2-tert-Butyl-4-methylphenoxy)-3,5,6-trichloro-phthalonitrile (2g), phthalonitrile (0.65g) 1,8-Diazabicycloundec-7-ene (1.9g) in a 100mL flask And 1-pentanol (15g) was added and heated to 90°C to melt the solid, then zinc acetate (0.47g) was added and stirred while heating to 140°C. After completion of the reaction, the precipitate is confirmed with methanol, followed by filtration and vacuum drying. The dried solid is purified by column chromatography. Dichloromethane is properly added to the solid obtained after purification to dissolve the solid, and then methanol is added to crystallize. The crystallized solid is filtered and vacuum-dried to obtain a compound represented by Chemical Formula 5-11.

[Formula 5-11]

Maldi-tof MS : 1109.03 m/z

(Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3: Synthesis of Binder Resin)

50 g of monomers for polymerization were sequentially added to a 200 ml beaker at a weight % ratio specified in Table 1 below. Thereafter, 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 weight average molecular weight (Mw) of each binder resin obtained as a result 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 Comparative Synthesis Example 1 Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 comparison
Synthesis Example 2 comparison
Synthesis Example 3 unit Acrylic acid 12 12 12 12 12 15 12 12 weight% Ethylhexylmethacrylate 37 - - - - - - - weight% Laurylmethacrylate - - 37 45 25 34 - - weight% Stearylmethacrylate - 37 - - - - - - weight% butylmethacrylate - - - - - - 37 - weight% methylmethacrylate - - - - - - - 37 weight% Dicyclopentanyl methacrylate 36 36 36 28 48 36 36 36 weight% Phenylmaleimdie 15 15 15 15 15 15 15 15 weight% Molecular Weight (Mw) 10,400 11,500 10,500 10,800 11,500 11,000 10,500 11,500 g/mol

(Examples 1 to 6 and Comparative Examples 1 to 5: Preparation of color filter composition)

The photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were prepared by mixing according to the compositions shown in Tables 2 and 3 below.

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.

ingredient solid content
(%) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 (A) Binder
profit
dispersion A-1 100 0.9 0.9 0.9 0.9 0.9 0.9 A-2 30 2.3 2.3 2.3 2.3 2.3 1.1 A-3 30 - - - - - A-4 30 6.4 - - - - A-5 30 - 6.4 - - - A-6 30 - - 6.4 - - A-7 30 - - - 6.4 - A-8 30 - - - - 6.4 7.6 A-9 30 - - - - - A-10 30 - - - - - (B) photopolymerizable compound B-1 100 5.2 5.2 5.2 5.2 5.2 5.2 (C) photopolymerization initiator C-1 100 0.6 0.6 0.6 0.6 0.6 0.6 (D) colorant dispersion D-1 20 3.0 3.0 3.0 3.0 3.0 3.0 D-2 20 17.9 17.9 17.9 17.9 17.9 17.9 D-3 5 31.3 31.3 31.3 31.3 31.3 31.3 (E) solvent E-1 - 32.2 32.2 32.2 32.2 32.2 32.2 (F) additives E-2 10 0.2 0.2 0.2 0.2 0.2 0.2

ingredient solid content
(%) comparative example
One comparative example
2 comparative example
3 comparative example
4 comparative example
5 (A) Binder
profit
dispersion A-1 100 0.9 0.9 0.9 0.9 0.9 A-2 30 2.3 8.7 2.3 2.3 - A-3 30 6.4 - - - - A-4 30 - - - - - A-5 30 - - - - 8.7 A-6 30 - - - - - A-7 30 - - - - - A-8 30 - - - - - A-9 30 - - 6.4 - - A-10 30 - - - 6.4 - (B) photopolymerizable compound B-1 100 5.2 5.2 5.2 5.2 5.2 (C) photopolymerization initiator C-1 100 0.6 0.6 0.6 0.6 0.6 (D) colorant dispersion D-1 20 3.0 3.0 3.0 3.0 3.0 D-2 20 17.9 17.9 17.9 17.9 17.9 D-3 5 31.3 31.3 31.3 31.3 31.3 (E) solvent E-1 - 32.2 32.2 32.2 32.2 32.2 (F) additives E-2 10 0.2 0.2 0.2 0.2 0.2

(A) binder resin dispersion

The dispersion medium is all PGMEA.

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

(A-2) Acrylic binder resin (product name: NPR5216, manufacturer: Miwon)

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

(A-4) Acrylic Composite Binder Resin (Synthesis Example 1)

(A-5) Acrylic Composite Binder Resin (Synthesis Example 2)

(A-6) Acrylic Composite Binder Resin (Synthesis Example 3)

(A-7) Acrylic Composite Binder Resin (Synthesis Example 4)

(A-8) Acrylic Composite Binder Resin (Synthesis Example 5)

(A-9) Acrylic Composite Binder Resin (Comparative Synthesis Example 2)

(A-10) Acrylic Composite Binder Resin (Comparative Synthesis Example 3)

(B) photopolymerizable compound

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

(C) photopolymerization initiator

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

(D) colorant dispersion

(D-1) green pigment dispersion (product name: AG1623 (G58), manufacturer: Sanyo)

(D-2) yellow pigment dispersion (product name: AG6451 (Y138), manufacturer: Sanyo)

(D-3) phthalocyanine-based dye dispersion (dye synthesis example 1)

(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 surface haze, heat resistance and chemical resistance were evaluated.

Evaluation 1: Surface haze of resin film

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, the sample was dried for 20 minutes in a hot air circulation drying furnace at 230° C. and dried once repeatedly to obtain a sample having the same thickness. The surface of the prepared sample was observed with an optical microscope to determine whether or not HAZE was present, and the results are shown in Table 4.

Evaluation 2: Heat resistance and chemical resistance of resin film

After making the sample prepared in Evaluation 1 into a size of 4 × 4 cm, immersing it in a PGMEA (propylene glycol methyl ether acetate) or NMP (N-methylpyrrolidone) solution at 25 ° C / 10 minutes to measure the color value before and after treatment It was measured using MCPD (Otsuka Co.) equipment.

The ΔEab* value, which is a measure of color change, was calculated by the following formula to analyze heat resistance and chemical resistance, and the results are shown in Table 4 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 1, the better the heat resistance and chemical resistance of the resin film.

Whether haze occurs ΔEab* PGMEA NMP Comparative Example 1 X 1.1 1.7 Comparative Example 2 X 2.8 2.9 Comparative Example 3 X 2.2 2.4 Comparative Example 4 X 2.0 2.3 Comparative Example 5 O 0.4 1.0 Example 1 X 0.7 1.3 Example 2 X 0.6 1.2 Example 3 X 0.5 1.1 Example 4 X 0.9 1.5 Example 5 X 0.7 1.4 Example 6 X 0.5 1.1

From Table 3, it can be seen that the photosensitive resin composition according to one embodiment does not generate haze on the surface of the resin film at the same or higher level than the photosensitive resin compositions of Comparative Examples 1 to 5. can

Furthermore, it can be seen that the photosensitive resin composition according to one embodiment has a small ΔEab* value in the same solvent and excellent heat resistance and chemical resistance, compared to the photosensitive resin compositions of Comparative Examples 1 to 5.

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 the detailed description of the invention and the accompanying drawings, and this is also the present invention. It goes without saying that it falls within the scope of the invention.

Claims (18)

(A) a binder resin dispersion;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
(D) a colorant dispersion; and
(E) solvent
Including,
The binder resin dispersion includes a binder resin and a first dispersion medium; The binder resin includes a first structural unit derived from a monomer represented by Formula 1 below;
the colorant dispersion includes a dye dispersion and a pigment dispersion; The dye dispersion includes a phthalocyanine-based dye and a second dispersion medium;
A photosensitive resin composition comprising 15 to 65 parts by weight of the first structural unit based on 100 parts by weight of the phthalocyanine-based dye:
[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 11 to 20 substituted or unsubstituted alkyl.
According to claim 1,
Of the total amount of the binder resin dispersion, the binder resin is included in 20 to 40% by weight photosensitive resin composition.
According to claim 1,
Of the total amount of the dye dispersion, the phthalocyanine-based dye is contained in 1 to 15% by weight photosensitive resin composition.
According to claim 1,
Of the total amount of the binder resin, the first structural unit is included in the photosensitive resin composition 15 to 50% by weight.
According to claim 1,
The binder resin may include a second structural unit derived from a monomer represented by Formula 2 below, a third structural unit derived from a monomer represented by Formula 3 below, a fourth structural unit derived from a monomer represented by Formula 4 below, or A photosensitive resin composition further comprising 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;
L is a single bond or an alkylene having 1 to 10 carbon atoms;
[Formula 4]

In Formula 4,
R ⁸ is hydrogen, alkyl of 1 to 10 carbon atoms, or aryl of 6 to 10 carbon atoms.
According to claim 5,
Of the total amount of the binder resin, the second structural unit is included in 5 to 30% by weight, the third structural unit is included in 15 to 60% by weight, and the fourth structural unit is included in 5 to 30% by weight 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,
Of the total amount of the binder dispersion, the binder resin is included in 20 to 40% by weight photosensitive resin composition.
According to claim 1,
The phthalocyanine-based dye is a photosensitive resin composition represented by Formula 5 below:
[Formula 5]

In Formula 5,
R ⁹ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C3 to C20 aryl group; A cyclic C6 to C20 aryloxy group;
However, at least one of R ⁹ to R ²⁴ is represented by the following formula (6);
[Formula 6]

In Formula 6,
R ²⁵ and R ²⁶ are each independently a halogen atom, an alkyl having 1 to 10 carbon atoms, or a branched-chain alkyl having 4 to 10 carbon atoms;
n1 and n2 are each independently an integer of 0 to 5, provided that 1 ≤ n1 + n2 ≤ 5.
According to claim 1,
Of the total amount of the dye dispersion, the phthalocyanine-based dye is contained in 1 to 15% by weight photosensitive resin composition.
According to claim 1,
The pigment dispersion is a photosensitive resin composition comprising a green pigment dispersion, a yellow pigment dispersion, or a combination thereof.
According to claim 11,
the green pigment dispersion includes a green pigment and a third dispersion medium; Of the total amount of the green pigment dispersion, the green pigment is contained in 10 to 30% by weight;
the yellow pigment dispersion includes a yellow pigment and a fourth dispersion medium; Of the total amount of the yellow pigment dispersion, the yellow pigment is contained in 10 to 30% by weight photosensitive resin composition.
According to claim 11,
Of the total amount of the colorant dispersion, the green pigment dispersion is included in 0.1 to 10% by weight, the yellow pigment dispersion is included in 10 to 25% by weight, and the phthalocyanine-based dye dispersion is included as the balance Photosensitive resin composition.
According to claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
1% to 15% by weight of the (A) binder resin dispersion;
0.1% to 10% by weight of the (B) photopolymerizable compound;
0.1% to 5% by weight of the (C) photopolymerization initiator; and
15% to 55% by weight of the (D) colorant dispersion; 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 16.
A display device comprising the color filter of claim 17 .