TWI826684B - Photosensitive resin composition, photosensitive resin layer and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition including (A) a colorant including a dye of a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the core is a squarylium-based compound and the shell is represented by Chemical Formula 1, a photosensitive resin layer manufactured using the same, and a color filter including the photosensitive resin layer. In Chemical Formula 1, each substituent is the same as defined in the specification.

Description

Photosensitive resin composition, photosensitive resin layer and color filter

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

This application claims priority and rights to Korean Patent Application No. 10-2019-0051681 filed with the Korean Intellectual Property Office on May 2, 2019, the entire content of which is incorporated herein by reference.

Among many types of displays, LCDs have the advantages of brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have become more widely used in laptops, monitors, and TV screens . The liquid crystal display device includes: a lower substrate on which a black matrix, a color filter and an ITO pixel electrode are formed; and an upper substrate on which an active circuit part and an ITO pixel electrode are formed, the active circuit part including a liquid crystal layer , thin film transistors and capacitor layers. The color filter is formed in the pixel area by sequentially stacking a plurality of pixel portions generally formed of three primary colors (such as red (R), green (G), and blue (B)) in a predetermined order to form each pixel, And the black matrix layer is disposed in a predetermined pattern on the transparent substrate to form boundaries between pixels.

The pigment dispersion method is one of the methods for forming color filters. A colored film is provided by repeating a series of processes as follows: a photopolymerizable composition containing a colorant is coated on a transparent substrate containing a black matrix, and is formed by exposure pattern, removing non-exposed parts with solvent, and thermally curing them. The colored photosensitive resin composition used to manufacture a color filter according to the pigment dispersion method generally contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, and the like. Pigment dispersion methods are actively used in the manufacture of LCDs such as mobile phones, laptops, monitors, and TVs. However, photosensitive resin compositions for color filters using pigment dispersion methods have recently been required to have improved performance and excellent pattern characteristics. Specifically, high color reproducibility and high brightness as well as high contrast ratio characteristics are urgently required.

An image sensor is a component used for photography in a mobile phone camera or digital still camera (DSC). Depending on the manufacturing process and application method, image sensors can be classified into charge-coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors. A color imaging device for a charge-coupled device image sensor or a complementary metal-oxide semiconductor image sensor includes color filters each having filter segments that mix primary colors of red, green, and blue, and the colors are separated of. Recent color filters installed in color imaging devices have a pattern size of 2 microns or less, which is 1/100 to 1/200 of the pattern size of conventional color filter patterns for LCDs. Therefore, increased resolution and reduced pattern residue are important factors in determining device performance.

Color filters manufactured by using a pigment-type photosensitive resin composition have limitations in brightness and contrast ratio due to the size of pigment particles. In addition, color imaging devices for image sensors require smaller dispersed particle sizes for forming fine patterns. In order to meet the requirements, efforts have been made to obtain a color filter with improved brightness and contrast ratio by introducing dyes that do not form particles instead of pigments, thereby preparing photosensitive resin compositions suitable for dyes. However, dyes have poor durability to pigments such as light resistance and heat resistance and the like, and thus brightness may be reduced.

Examples provide photosensitive resin compositions with improved brightness and durability.

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

Another embodiment provides a color filter including a photosensitive resin layer.

Embodiments provide a photosensitive resin composition, which includes: (A) a colorant, including a dye with a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound (photopolymerizable monomer); (D) a photopolymerization initiator; and (E) a solvent, wherein the core is an aromatic cyanine compound and the shell is represented by Chemical Formula 1.

[Chemical formula 1] In Chemical Formula 1, R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group, * is the bonding position), R ² to R ⁵ are independently hydrogen atoms or substituted or unsubstituted C1 to C20 alkyl groups, with the proviso that R ¹ to R ⁵ are not hydrogen atoms at the same time, m is 1 to 10 n is an integer from 0 to 3, and L ¹ and L ² are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The shell can be represented by Chemical Formula 2.

[Chemical formula 2] In Chemical Formula 2, R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group, * is the bonding position), R ² to R ⁵ are independently hydrogen atoms or substituted or unsubstituted C1 to C20 alkyl groups, with the proviso that R ¹ to R ⁵ are not hydrogen atoms at the same time, and n is 0 to an integer of 3.

The shell may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-3.

[Chemical formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] In Chemical Formula 2-1 to Chemical Formula 2-3, R ² to R ⁵ are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and R ⁷ and R ⁸ are independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl or *-OR ⁶ (where R ⁶ is substituted or unsubstituted C1 to C20 alkyl and * is the bonding position).

The shell may have a cage width of 6.5 Angstroms to 7.5 Angstroms.

The shell may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-4. [Chemical formula 3-1] [Chemical formula 3-2] [Chemical formula 3-3] [Chemical formula 3-4]

Aromatic cyanine compounds can be represented by Chemical Formula 4. [Chemical formula 4] In Chemical Formula 4, R ⁹ to R ¹² are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 Aryl.

The core can have a length of 1 nanometer to 3 nanometers.

The core may have a maximum absorption peak in the wavelength of 530 nanometers to 680 nanometers.

The aromatic cyanine compound may be represented by one of Chemical Formula 4-1 to Chemical Formula 4-6. [Chemical formula 4-1] [Chemical formula 4-2] [Chemical formula 4-3] [Chemical formula 4-4] [Chemical formula 4-5] [Chemical formula 4-6]

Dyes of core-shell structure may contain core and shell in a molar ratio of 1:1.

The core-shell structured dye may be a green dye.

Colorants may further include pigments.

The photosensitive resin composition may include 0.5% to 20% by weight of colorant; 0.1% to 30% by weight of binder resin; and 0.1% to 30% by weight of photosensitive resin based on the total amount of the photosensitive resin composition. Polymer compound (monomer); 0.1% to 5% by weight of photopolymerization initiator; and the balance solvent.

The photosensitive resin composition may further include malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a free radical polymerization initiator or a combination thereof, and the silane coupling agent The mixture contains vinyl or (meth)acryloxy groups.

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

Another embodiment provides a color filter including a photosensitive resin layer.

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

The photosensitive resin composition according to the embodiment can implement a color filter with improved brightness and durability by using a core-shell dye including a shell having a special structure surrounding an aroocyanine core.

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary and the present invention is not limited thereto and the present invention is defined by the scope of the claimed claims.

In this specification, when no specific definition is otherwise provided, "substituted" means replacement of at least one hydrogen of a compound by a substituent selected from the following: a halogen atom (F, Cl, Br or I), a hydroxyl group, C1 to C20 Alkoxy group, nitro group, cyano group, amino group, imino group, azido group, amidino group, hydrazino group, hydrazino 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, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, and combinations thereof.

In this specification, when no special definition is provided otherwise, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkyl" refer to those containing N, O, S or Cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl cyclic compounds with at least one heteroatom in P.

In this specification, "(meth)acrylate" refers to both "acrylate" and "methacrylate" when no special definition is otherwise provided.

In this specification, "combination" means mixing or copolymerization when no specific definition is otherwise provided.

In this specification, when a definition is not otherwise provided, in a chemical formula, when a chemical bond is not drawn, hydrogen is bonded at the position given presumably.

In this specification, when no special definition is otherwise provided, "*" indicates a point where the same or different atoms or chemical formulas are bonded.

The photosensitive resin composition according to the embodiment includes: (A) a colorant, a dye including a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) A solvent in which the core is an aromatic cyanine compound and the shell is represented by Chemical Formula 1.

[Chemical formula 1] In Chemical Formula 1, R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group, * is the bonding position), R ² to R ⁵ are independently hydrogen atoms or substituted or unsubstituted C1 to C20 alkyl groups, with the proviso that R ¹ to R ⁵ are not hydrogen atoms at the same time, m is 1 to 10 n is an integer from 0 to 3, and L ¹ and L ² are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

In Chemical Formula 1, L ¹ and L ² may independently be substituted or unsubstituted C1 to C10 alkylene group. In this case, solubility is improved and structures are readily formed in which a shell surrounds the arocyanine compound.

For example, the core-shell dye according to the embodiment includes a non-covalent bond, that is, a hydrogen bond, between the oxygen atom of the arocyanine compound and the hydrogen atom bonded to the nitrogen atom of the shell represented by Chemical Formula 1.

In general, arocyanines are often used as green dyes because of their improved green spectral properties and high molar absorption coefficient. However, after manufacturing a color resist that has poor durability compared to pigments, the brightness may decrease during the baking process. In the photosensitive resin composition according to the embodiment, a core-shell structure compound in which the shell represented by Chemical Formula 1 uses an aromatic cyanine compound is used as the colorant instead of the conventional aromatic acid cyanine compound. Serves as a nucleus to form a core-shell structure. The core-shell structure compound is used as a colorant to improve the durability of the color filter, thereby realizing a color filter with high brightness and high contrast ratio.

Hereinafter, each component is specifically described. (A) Colorant

The photosensitive resin composition according to the embodiment contains a dye with a core-shell structure.

As described above, in the color filter made of the pigment-type photosensitive resin composition, there are limitations on brightness and contrast ratio due to the pigment particle size. In addition, for application to image sensors, a resin composition composed of smaller particles is required for forming fine patterns. To achieve this purpose, efforts have been made to implement a color filter with improved brightness and contrast ratio by introducing a dye that does not form particles instead of a pigment to prepare a photosensitive resin composition suitable for the dye. However, dyes have weak durability compared to pigments, and thus have limitations in improving brightness and contrast ratio.

However, in the case of the dye used as a colorant in the photosensitive resin composition according to the embodiment, the center of the aromatic cyanine compound having excellent green spectral characteristics and high molar extinction coefficient is represented by Chemical Formula 1 Surrounded by a cyclic compound, the durability can be improved more compared to a pigment-type photosensitive resin composition and a dye-type photosensitive resin composition to implement a color filter with brightness and contrast ratio.

Specifically, the core-shell dye has a structure composed of an aro cyanine core and a shell surrounding the core, and the aro cyanine core is surrounded by the shell of the macrocyclic compound represented by Chemical Formula 1 to form a coating. Due to this structure, that is, by having a structure in which the aromatic cyanine compound is present in the ring represented by Chemical Formula 1, the durability of the dye having a core-shell structure can be improved and thus it is possible to implement a dye with high brightness and High contrast ratio color filter.

For example, the shell can be represented by Chemical Formula 2.

[Chemical formula 2] In Chemical Formula 2, R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group, * is the bonding position), R ² to R ⁵ are independently hydrogen atoms or substituted or unsubstituted C1 to C20 alkyl groups, with the proviso that R ¹ to R ⁵ are not hydrogen atoms at the same time, and n is 0 to an integer of 3.

For example, in Chemical Formula 1 and Chemical Formula 2, R ¹ may be a hydrogen atom, and R ² to R ⁵ may independently be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, with the limitation that R ² At least one of R ⁵ is substituted or unsubstituted C1 to C20 alkyl.

For example, in Chemical Formula 1 and Chemical Formula 2, R ¹ may be a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group C20 alkyl, * is the bonding position), R ² to R ⁵ are independently hydrogen atoms.

For example, R ¹ can be a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group, and * is a bond position), and at least one of R ² to R ⁵ may be substituted or unsubstituted C1 to C20 alkyl.

For example, Chemical Formula 2 can be represented by Chemical Formula 2A. [Chemical Formula 2A] In Chemical Formula 2A, R ¹ is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or *-OR ⁶ (where R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group, and * is a bond position), and R ² to R ⁵ are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the shell may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-3. [Chemical formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] In Chemical Formula 2-1 to Chemical Formula 2-3, R ² to R ⁵ are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and R ⁷ and R ⁸ are independently a halogen atom, a substituted or Unsubstituted C1 to C20 alkyl or *-OR ⁶ (where R ⁶ is substituted or unsubstituted C1 to C20 alkyl and * is the linkage position).

For example, the shell may have a cage width of 6.5 to 7.5 Angstroms and a volume of 10 to 16 Angstroms. The cage width in the present invention refers to the internal distance of the shell, for example the distance between two different phenylene groups bonding two methylene groups in the shell represented by Chemical Formula 2 (see Figure 1). When the shell has a cage width within the range, a core-shell dye having a structure surrounding an aromatic cyanine compound can be obtained, and thus when the core-shell dye is used as a colorant of a photosensitive resin composition, it can Implemented color filters with improved durability and high brightness.

For example, the shell may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-4, but is not limited thereto. [Chemical formula 3-1] [Chemical formula 3-2] [Chemical formula 3-3] [Chemical formula 3-4]

For example, in a core-shell dye, the arocyanine compound constituting the core can be represented by Chemical Formula 4. [Chemical formula 4] In Chemical Formula 4, R ⁹ to R ¹² are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 Aryl.

For example, in Chemical Formula 4, R ⁹ and R ¹¹ may independently be substituted or unsubstituted C1 to C20 alkyl or substituted or unsubstituted C3 to C20 cycloalkyl, and R ¹⁰ and R ¹² may independently be substituted or unsubstituted C6 to C20 aryl.

For example, R ⁹ and R ¹¹ may independently be "C1 to C20 alkoxy substituted or unsubstituted from C1 to C10 alkoxy" or "Substituted or unsubstituted from C1 to C10 alkoxy C3 to C20 cycloalkyl”.

For example, the C1 to C10 alkoxy group may be an unsubstituted C1 to C10 alkoxy group or a C1 to C6 alkoxy group substituted by a C1 to C4 alkyl group.

The compound represented by Chemical Formula 4 has three types of resonance structures as illustrated in the following drawings, but in this specification, the compound having one type of resonance structure and represented by Chemical Formula 4 is illustrated for convenience. In other words, the compound represented by Chemical Formula 4 may have any one of three types of resonance structures.

For example, the core (that is, the aromatic cyanine compound) may be represented by one of Chemical Formula 4-1 to Chemical Formula 4-6, but is not limited thereto. [Chemical formula 4-1] [Chemical formula 4-2] [Chemical formula 4-3] [Chemical formula 4-4] [Chemical formula 4-5] [Chemical formula 4-6]

For example, when the compound represented by Chemical Formula 4-1 to Chemical Formula 4-6, and specifically the compound represented by Chemical Formula 4-6 is used in a photosensitive resin composition (for example, as a dye), the subsequently described The solubility in solvents may be greater than or equal to 5, such as 5 to 10. Solubility can be obtained by the amount (grams) of dye (compound) dissolved in 100 grams of solvent. When the compound (for example, a dye) has solubility within the range, it is possible to ensure that it is compatible with other components in the photosensitive resin composition (that is, a binder resin, a photopolymerizable monomer, and a photopolymerizable resin to be described later). Starting agent) compatibility and coloring properties, and can prevent dye precipitation.

For example, the compounds represented by Chemical Formula 4-1 to Chemical Formula 4-6 may have improved heat resistance. That is to say, the thermal decomposition temperature measured using a thermogravimetric analyzer (TGA) may be greater than or equal to 200°C, for example, 200°C to 300°C.

The length of the compound represented by Chemical Formula 4 contained in or composed of the core may be 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the compound represented by Chemical Formula 4 has a length within the range, a core-shell structure can be easily formed. In other words, the compound represented by Chemical Formula 4 has a length within the range and thus can easily form a structure in which the shell that is the macrocyclic compound represented by Chemical Formula 1 surrounds the compound represented by Chemical Formula 4. When a compound having a length outside the range is used, a structure in which the shell does not surround the core compound may not be obtained, and durability may not be improved.

For example, the core-shell structure compound may have a maximum absorption peak in a wavelength of 530 nanometers to 680 nanometers. A dye having a core-shell structure with spectral characteristics is used, for example, as a green dye and thereby a photosensitive resin composition for a color filter having high brightness and high contrast ratio can be provided.

For example, the core-shell structure compound may include an arocyanine core and a shell with a molar ratio of 1:1. When the core and shell are present in the molar ratio, the coating (shell) surrounding the arocyanine core can be better formed.

For example, the core-shell structure dye may be represented by one of the compounds represented by Chemical Formula 5-1 to Chemical Formula 5-24, but is not limited thereto. [Chemical formula 5-1] [Chemical formula 5-2] [Chemical formula 5-3] [Chemical formula 5-4] [Chemical formula 5-5] [Chemical formula 5-6] [Chemical formula 5-7] [Chemical formula 5-8] [Chemical formula 5-9] [Chemical formula 5-10] [Chemical formula 5-11] [Chemical formula 5-12] [Chemical formula 5-13] [Chemical formula 5-14] [Chemical formula 5-15] [Chemical formula 5-16] [Chemical formula 5-17] [Chemical formula 5-18] [Chemical formula 5-19] [Chemical formula 5-20] [Chemical formula 5-21] [Chemical formula 5-22] [Chemical formula 5-23] [Chemical formula 5-24]

Core-shell dyes can be used alone as green dyes and mixed with auxiliary dyes.

Auxiliary dyes can be triarylmethane dyes, anthraquinone dyes, benzyl dyes, cyanine dyes, phthalocyanine dyes, azaporphyrin dyes, Indigo dyes, xanthene dyes, pyridone azo dyes and the like.

Core-shell dyes can be mixed with pigments. That is, the colorant may further include a pigment.

The pigments may be red pigments, green pigments, blue pigments, yellow pigments, black pigments and the like.

Examples of the red pigment may be C.I. red pigment 254, C.I. red pigment 255, C.I. red pigment 264, C.I. red pigment 270, C.I. red pigment 272, C.I. red pigment 177, C.I. red pigment 89, and the like. Examples of the green pigment may be C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green Pigment 59, and the like. Examples of blue pigments may be copper phthalocyanine pigments, such as C.I. Blue Pigment 15:6, C.I. Blue Pigment 15, C.I. Blue Pigment 15:1, C.I. Blue Pigment 15:2, C.I. Blue Pigment 15:3 , C.I. Blue Pigment 15:4, C.I. Blue Pigment 15:5, C.I. Blue Pigment 16 and the like. Examples of yellow pigments may be isoindoline pigments such as C.I. Yellow Pigment 139 and the like; quinoline yellow pigments such as C.I. Yellow Pigment 138 and the like; nickel complex pigments such as C.I. Yellow Pigment 150 and the like things. Examples of black pigments may be aniline black, perylene black, titanium black, carbon black and the like. The pigments may be used alone or in a mixture of two or more and are not limited thereto.

The pigment can be contained in the photosensitive resin composition for the color filter in the state of a pigment dispersion. Pigment dispersions may be composed of pigments and solvents, dispersants, dispersion resins, and the like.

The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like, and ideally It is propylene glycol methyl ether acetate.

Dispersants assist in the uniform dispersion of the pigment and may include nonionic, anionic or cationic dispersants. Specific examples may be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate ester, sulfonate salt, carboxylate ester, carboxylic acid Salts, alkylamide alkylene oxide addition products, alkylamines, and can be used alone or in a mixture of two or more.

The dispersion resin may be an acrylic resin containing carboxyl groups, and improves the stability of the pigment dispersion and the pattern characteristics of the pixels.

When mixing the core-shell dye and the pigment, the core-shell dye and the pigment may be mixed in a weight ratio of 1:9 to 9:1, and specifically in a weight ratio of 3:7 to 7:3. When mixed core-shell dyes and pigments are mixed within the stated weight ratio range, high brightness and contrast ratios can be achieved while maintaining color characteristics.

The colorant may be included in an amount of 0.5% to 20% by weight (for example, 1% to 15% by weight) based on the total amount of the photosensitive resin composition. When the colorant is used within the stated range, high brightness and high contrast ratio at the desired color coordinates can be achieved. (B) Binder resin

The binder resin may be a copolymer of a first ethylenically unsaturated monomer, a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and a resin containing at least one acrylic repeating unit. .

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group. Examples of monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight (eg, 10% to 40% by weight) based on the total amount of the alkali-soluble resin.

Examples of the second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether, and the like; unsaturated carboxylic acid ester compounds , such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Benzyl acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate and the like; unsaturated carboxylic acid aminoalkyl ester compounds, such as 2-aminoethyl (meth)acrylate, (meth)acrylate 2-dimethylaminoethyl methacrylate and the like; carboxylic acid vinyl ester compounds, such as vinyl acetate, vinyl benzoate and the like; unsaturated carboxylic acid glycidyl ester compounds, such as (methyl) Glycidyl acrylate and the like; vinyl cyanide compounds, such as (meth)acrylonitrile and the like; unsaturated amide compounds, such as (meth)acrylamide and the like; and the like, and the above Examples of the diene unsaturated monomer may be used alone or in a mixture of two or more.

Examples of the binder resin may include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/methacrylic acid 2-hydroxyethyl ester copolymer, methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and examples of the binder resin may Used alone or in a mixture of two or more.

The binder resin may have a weight average molecular weight of 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol or 20,000 g/mol to 30,000 g/mol. When the binder resin has a weight average molecular weight within the stated range, the composition can have excellent close contact characteristics with the substrate, good physical and chemical properties, and appropriate viscosity.

The binder resin may have an acid value of 15 mg KOH/g to 60 mg KOH/g, such as 20 mg KOH/g to 50 mg KOH/g. When the binder resin has an acid value within the range, it can result in excellent pixel resolution.

The binder resin may be included in an amount of 0.1% to 30% by weight (for example, 5% to 20% by weight) based on the total amount of the photosensitive resin composition. When the binder resin within the range is included, the composition can have excellent developability and improved cross-linking, and thus have excellent surface flatness when manufactured into a color filter. (C) Photopolymerizable monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

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

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate ) Acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di (Meth)acrylate, Pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Dipentaerythritol di(meth)acrylate Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol mono Methyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, aldehyde epoxy (meth)acrylate, and the like.

Commercially available examples of reactive unsaturated compounds are as follows. Monofunctional (meth)acrylates may include Aronix M- ^101® , M- ^111® , M- ^114® (Toagosei Chemistry Industry Co., Ltd.); card KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic Chemical Industry Co., Ltd.) Organic Chemical Ind., Ltd.)) and the like. Examples of bifunctional (meth)acrylates may include Anix M-210 ^® , M-240 ^® , M-6200 ^® (East Asia Synthetic Chemical Industry Co., Ltd.), Cayard HDDA ^® , HX-220 ^® , R-604 ^® (Nippon Kayaku Co., Ltd.), V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Industry Co., Ltd.) and the like. Examples of trifunctional (meth)acrylates may include Anix M- ^309® , M- ^400® , M- ^405® , M- ^450® , M- ^7100® , M- ^8030® , M- ^8060® ( Toa Synthetic Chemical Industry Co., Ltd.), Cayard TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (Nippon Kayaku Co., Ltd.), V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Yuki Kayaku Kogyo Co. Ltd.) and the like. These may be used alone or in a mixture of two or more.

Photopolymerizable monomers can be treated with anhydrides to improve developability.

The photopolymerizable monomer may be included in an amount of 0.1% to 30% by weight (eg, 5% to 20% by weight) based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the range, pattern characteristics and developability can be improved during color filter manufacturing. (D) Photopolymerization initiator

The photopolymerization initiator may include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, and oxime compounds. and the like.

Examples of acetophenones may include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (Methylthio)phenyl)-2-morpholinylpropan-1-one, 2-phenylmethyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, and Analogues.

Examples of benzophenones may be benzophenone, benzoyl benzoate, benzoyl methylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated diphenyl Methone, 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 thioxanthone compounds may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

Examples of benzoin compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, and the like.

Examples of triazine compounds may include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyrene)-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-(naphthol)-4 ,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxystyryl)-6-triazine and the like.

Examples of oxime compounds may include 2-(o-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyl oxime)-1 -[9-ethyl-6-(2-methylbenzoyl)-9H-terazol-3-yl]ethanone and the like.

In addition to the above compounds, the photopolymerization initiator may include carbazole compounds, diketone compounds, stodium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene ( fluorene) compounds and analogs.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight (for example, 1% to 3% by weight) based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the range, the composition can sufficiently photopolymerize when exposed during the pattern formation process for preparing a color filter, thereby achieving excellent sensitivity and improving transmittance. (E) Solvent

The solvent is not particularly limited, but examples of the solvent include alcohols such as methanol, ethanol and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenylene ether, tetrahydrofuran and the like; Glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether and the like; cellosolve acetate, such as cellosolve methyl acetate, cellosolve ethyl acetate, cellosolve diacetate Ethyl esters and analogs; carbitols (carbitols), such as methylethyl carbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether and the like; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; aromatic Hydrocarbons, such as toluene, xylene and similar; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone , methyl-n-pentanone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate and the like; lactate alkyl esters, such as Methyl lactate, ethyl lactate, and the like; alkyl glycolates, such as methyl glycolate, ethyl glycolate, butyl glycolate, and the like; alkoxyalkyl acetates, such as methoxymethyl acetate Esters, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate and the like; 3-hydroxypropionic acid alkyl esters, such as 3-hydroxypropionic acid methyl ester , ethyl 3-hydroxypropionate and similar; alkyl 3-alkoxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Ethyl acid ester, methyl 3-ethoxypropionate and the like; alkyl 2-hydroxypropionate, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate and analogs; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy methyl propionate and the like; alkyl 2-hydroxy-2-methylpropionate, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and Analogues; alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and Analogues; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, and the like; or ketones Acid ester compounds, such as ethyl pyruvate. In addition, the solvent may be N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl styrene, benzyl ether, dihexyl ether, acetylacetone, isophorone (isophorone), hexanoic acid, caprylic acid, 1-octanol, 1-nonan Alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, cellosolve Phenyl acetate and the like. These may be used alone or in a mixture of two or more.

In consideration of blendability, reactivity and similar properties, the solvent may include glycol ethers such as ethylene glycol monoethyl ether and the like; glycol alkyl ether acetates such as cellosolve ethyl acetate and the like; Esters, such as 2-hydroxyethyl propionate and the like; diethylene glycol, such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propylene glycol Ether acetates and the like.

The solvent may be included in the balance and specifically in an amount of 20 to 90% by weight based on the total amount of the photosensitive resin composition.

When the solvent within the range is included, the photosensitive resin composition can have excellent coating characteristics and maintain excellent flatness in a layer with a thickness of 3 micrometers or more. (F) Other additives

The photosensitive resin composition may further include other additives, such as malonic acid; 3-amino-1,2-propanediol; silane coupling agents containing vinyl or (meth)acryloxy groups; leveling agents; fluorine compounds Surfactant; radical polymerization initiator, in order to prevent stains or spots during coating, in order to adjust leveling, or in order to prevent pattern residues due to non-development.

The photosensitive resin composition may further include an epoxy compound in order to improve close contact characteristics with the substrate.

Examples of the epoxy compound may include phenol novolac epoxy compound, tetramethylbiphenyl epoxy compound, bisphenol A epoxy compound, alicyclic epoxy compound, or combinations thereof.

The amount of additive used can be controlled depending on the desired properties.

Another embodiment provides a photosensitive resin layer produced using the aforementioned photosensitive resin composition.

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

Coating a bare glass substrate or a glass substrate with a protective layer ( _SiN Thick photosensitive resin composition for color filters. After coating, the composition is irradiated with light to form the desired pattern for the color filter. After irradiation with light, the coating is treated with an alkaline developer and its non-irradiated areas can be dissolved to form a pattern for a color filter. This process is repeated depending on the number of R, G, and B colors required, thereby producing a color filter with the desired pattern.

In addition, the image pattern obtained by development is cured by heat treatment, actinic ray irradiation or the like, thereby improving crack resistance, solvent resistance and the like.

Hereinafter, the invention is explained in more detail with reference to examples. However, these examples should not be construed in any sense as limiting the scope of the invention. (Preparation of single-molecule compounds) ( Preparation Example 1 : Preparation of Intermediate A ) Intermediate A

Aniline (10 moles), 4-bromotoluene (10 moles), Pd ₂ (dba) ₃ (0.1 moles) and Xphos (0.1 moles) were added to toluene, heated at 100°C, and then stirred for 24 hours. Ethyl acetate was added thereto and washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain Intermediate A. ( Preparation Example 2 : Preparation of Intermediate B-1 ) Intermediate B-1

2,4-Dimethyldiphenylamine (10 moles), 1,2-epoxyhexane (12 moles), and sodium hydride (12 moles) were added to N,N-dimethylformamide ( DMF), heated at 90°C, and then stirred for 24 hours. Ethyl acetate was added thereto and washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate B-1. ( Preparation Example 3 : Preparation of Intermediate B-2 ) Intermediate B-2

Intermediate B-2 was obtained according to the same method as Preparation Example 2 except that 1,2-epoxybutane was used instead of 1,2-epoxyhexane. ( Preparation Example 4 : Preparation of Intermediate B-3 ) Intermediate B-3

Intermediate B-3 was obtained according to the same method as Preparation Example 2 except that intermediate A was used instead of 2,4-dimethyldiphenylamine. ( Preparation Example 5 : Preparation of Intermediate B-4 ) Intermediate B-4

Intermediate B-4 was obtained according to the same method as Preparation Example 2 except that 1,2-epoxycyclohexane was used instead of 1,2-epoxyhexane. ( Preparation Example 6 : Preparation of Intermediate C-1 ) Intermediate C-1

Intermediate B-1 (10 mmol), methyl iodide (15 mmol) and sodium hydride (15 mmol) were added to N,N-dimethylformamide and stirred at room temperature for 24 hours. . Ethyl acetate was added thereto and washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate C-1. ( Preparation Example 7 : Preparation of Intermediate C-2 ) Intermediate C-2

The compound represented by intermediate C-2 was obtained according to the same method as Preparation Example 6 except that 2-iodopropane was used instead of methyl iodide. ( Preparation Example 8 : Preparation of Intermediate C-3 ) Intermediate C-3

The compound represented by intermediate C-3 was obtained according to the same method as Preparation Example 6, except that intermediate B-2 was used instead of intermediate B-1. ( Preparation Example 9 : Preparation of Intermediate C-4 ) Intermediate C-4

The compound represented by intermediate C-4 was obtained according to the same method as Preparation Example 8 except that ethyl iodide was used instead of methyl iodide. ( Preparation Example 10 : Preparation of Intermediate C-5 ) Intermediate C-5

The compound represented by intermediate C-5 was obtained according to the same method as Preparation Example 6, except that intermediate B-4 was used instead of intermediate B-1. ( Preparation Example 11 : Preparation of Intermediate C -6 ) Intermediate C-6

The compound represented by intermediate C-6 was obtained according to the same method as Preparation Example 10 except that 1-iodo-2-ethylhexane was used instead of methyl iodide. ( Preparation Example 12 : Preparation Chemical Formula 4-1 )

Intermediate C-1 (60 mmol) and 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30 mmol) were added to toluene (200 ml) and butanol (200 ml) and refluxed to obtain the product, and the product was removed using a Dean-stark distillation apparatus. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain the compound represented by Chemical Formula 4-1. ( Preparation Example 13 : Preparation Chemical Formula 4-2 )

The compound represented by Chemical Formula 4-2 was obtained according to the same method as Preparation Example 12 except that intermediate C-2 was used instead of intermediate C-1. ( Preparation Example 14 : Preparation Chemical Formula 4-3 )

The compound represented by Chemical Formula 4-3 was obtained according to the same method as Preparation Example 12 except that intermediate C-3 was used instead of intermediate C-1. ( Preparation Example 15 : Preparation Chemical Formula 4-4 )

The compound represented by Chemical Formula 4-4 was obtained according to the same method as Preparation Example 12 except that intermediate C-4 was used instead of intermediate C-1. ( Preparation Example 16 : Preparation Chemical Formula 4-5 )

The compound represented by Chemical Formula 4-5 was obtained according to the same method as Preparation Example 12 except that intermediate C-5 was used instead of intermediate C-1. ( Preparation Example 17 : Preparation Chemical Formula 4-6 )

The compound represented by Chemical Formula 4-6 was obtained according to the same method as Preparation Example 12 except that intermediate C-6 was used instead of intermediate C-1. ( Preparation of core - shell dye ) ( Synthesis example 1 : Synthesis chemical formula 5-1 )

The compound represented by Chemical Formula 4-1 (5 mmol) was dissolved in 600 ml of chloroform solvent, and then triethylamine (TEA) (50 mmol) was added thereto. 2,6-pyridinedicarbonyldichloride (20 mmol) and (2,3,5,6-tetramethyl-1,4-phenylene)dimethaneamine (20 mmol) were dissolved in into 60 ml of chloroform and added simultaneously dropwise over 5 hours at room temperature. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 5-1. Maldi-tof MS: 1346.75m/z ( Synthesis Example 2 : Synthesis Chemical Formula 5-2 )

The compound represented by Chemical Formula 5-2 was obtained according to the same method as Synthesis Example 1, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS : 1402.82m/z ( Synthesis Example 3 : Synthesis Chemical Formula 5-3 )

The compound represented by Chemical Formula 5-3 was obtained according to the same method as Synthesis Example 1, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1290.60m/z ( Synthesis Example 4 : Synthesis Chemical Formula 5-4 )

The compound represented by Chemical Formula 5-4 was obtained according to the same method as Synthesis Example 1, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1318.72m/z ( Synthesis Example 5 : Synthesis Chemical Formula 5-5 )

The compound represented by Chemical Formula 5-5 was obtained according to the same method as Synthesis Example 1, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1342.72m/z ( Synthesis Example 6 : Synthesis Chemical Formula 5-6 )

The compound represented by Chemical Formula 5-6 was obtained according to the same method as Synthesis Example 1, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1538.94m/z ( Synthesis Example 7 : Synthesis Chemical Formula 5-7 )

The compound represented by Chemical Formula 4-1 (5 mmol) was dissolved in 600 ml of chloroform solvent, and then triethylamine (50 mmol) was added thereto. Dissolve 2,6-pyridinedicarbonyl dichloride (20 mmol) and (2-methyl-1,4-phenyl)dimethaneamine (20 mmol) in 60 ml of chloroform and incubate in room Add simultaneously in a dropwise manner at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 5-7. Maldi-tof MS: 1262.66m/z ( Synthesis Example 8 : Synthesis Chemical Formula 5-8 )

The compound represented by Chemical Formula 5-8 was obtained according to the same method as Synthesis Example 7, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1318.72m/z ( Synthesis Example 9 : Synthesis Chemical Formula 5-9 )

The compound represented by Chemical Formula 5-9 was obtained according to the same method as Synthesis Example 7, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1206.59m/z ( Synthesis Example 10 : Synthesis Chemical Formula 5-10 )

The compound represented by Chemical Formula 5-10 was obtained according to the same method as Synthesis Example 7, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1234.63m/z ( Synthesis Example 11 : Synthesis Chemical Formula 5-11 )

The compound represented by Chemical Formula 5-11 was obtained according to the same method as Synthesis Example 7, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1258.63m/z ( Synthesis Example 12 : Synthesis Chemical Formula 5-12 )

The compound represented by Chemical Formula 5-12 was obtained according to the same method as Synthesis Example 7, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1454.84m/z ( Synthesis Example 13 : Synthesis Chemical Formula 5-13 )

The compound represented by Chemical Formula 4-1 (5 mmol) was dissolved in 600 ml of chloroform solvent, and then triethylamine (50 mmol) was added thereto. 4-Trifluoromethylpyridine-2,6-dicarbonyldichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 ml of chloroform and added dropwise at room temperature. The method is added simultaneously and lasts 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 5-13. Maldi-tof MS: 1370.60m/z ( Synthesis Example 14 : Synthesis Chemical Formula 5-14 )

The compound represented by Chemical Formula 5-14 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1426.66m/z ( Synthesis Example 15 : Synthesis Chemical Formula 5-15 )

The compound represented by Chemical Formula 5-15 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1314.54m/z ( Synthetic Example 16 : Synthetic Chemical Formula 5-16 )

The compound represented by Chemical Formula 5-16 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1342.57m/z ( Synthetic Example 17 : Synthetic Chemical Formula 5-17 )

The compound represented by Chemical Formula 5-17 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1366.57m/z ( Synthesis Example 18 : Synthesis Chemical Formula 5-18 )

The compound represented by Chemical Formula 5-18 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1562.79m/z ( Synthesis Example 19 : Synthesis Chemical Formula 5-19 )

The compound represented by Chemical Formula 4-1 (5 mmol) was dissolved in 600 ml of chloroform solvent, and then triethylamine (50 mmol) was added thereto. 2-Ethylhexyloxypyridine-2,6-dicarbonyldichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 ml of chloroform and incubated successively at room temperature. The drip method is added simultaneously for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 5-19. Maldi-tof MS: 1490.87m/z ( Synthesis Example 20 : Synthesis Chemical Formula 5-20 )

The compound represented by Chemical Formula 5-20 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-2 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1546.93m/z ( Synthesis Example 21 : Synthesis Chemical Formula 5-21 )

The compound represented by Chemical Formula 5-21 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-3 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1434.80m/z ( Synthesis Example 22 : Synthesis Chemical Formula 5-22 )

The compound represented by Chemical Formula 5-22 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-4 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1462.83m/z ( Synthesis Example 23 : Synthesis Chemical Formula 5-23 )

The compound represented by Chemical Formula 5-23 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-5 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1486.83m/z ( Synthesis Example 24 : Synthesis Chemical Formula 5-24 )

The compound represented by Chemical Formula 5-24 was obtained according to the same method as Synthesis Example 13, except that the compound represented by Chemical Formula 4-6 was used instead of the compound represented by Chemical Formula 4-1. Maldi-tof MS: 1683.05m/z (Comparative synthesis example 1 )

The compound represented by Chemical Formula 4-1 (5 mmol) was dissolved in 600 ml of chloroform solvent, and then triethylamine (50 mmol) was added thereto. 2,6-Pyridinedicarbonyldichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 ml of chloroform and added simultaneously dropwise over 5 hours at room temperature. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell structure compound. ( Preparation of photosensitive resin composition )

A photosensitive resin composition is prepared using the following components. (A) Colorant (dye) (A-1) Core-shell dye prepared in Synthesis Example 1 (represented by Chemical Formula 5-1) (A-2) Core-shell dye prepared in Synthesis Example 2 (expressed by Chemical Formula 5 -2) (A-3) Synthesis of the core-shell dye prepared in Example 3 (expressed by Chemical Formula 5-3) (A-4) Synthesis of the core-shell dye prepared in Example 4 (expressed by Chemical Formula 5-4) (A-5) Synthesis of the core-shell dye prepared in Example 5 (expressed by Chemical Formula 5-5) (A-6) Synthesis of the core-shell dye prepared in Example 6 (expressed by Chemical Formula 5-6) (A-7 ) Core-shell dye prepared in Synthesis Example 7 (expressed by Chemical Formula 5-7) (A-8) Core-shell dye prepared in Synthesis Example 8 (expressed by Chemical Formula 5-8) (A-9) Synthesis Example 9 Core-shell dye prepared in Synthesis Example 10 (expressed by Chemical Formula 5-9) (A-10) Core-shell dye prepared in Synthesis Example 10 (expressed by Chemical Formula 5-10) (A-11) Core prepared in Synthesis Example 11 - Shell dye (represented by Chemical Formula 5-11) (A-12) Core-shell dye prepared in Synthesis Example 12 (represented by Chemical Formula 5-12) (A-13) Core-shell dye prepared in Synthesis Example 13 ( (Represented by Chemical Formula 5-13) (A-14) Synthesis of the core-shell dye prepared in Example 14 (Represented by Chemical Formula 5-14) (A-15) Synthesis of the core-shell dye prepared in Example 15 (Represented by Chemical Formula 5- 15) (A-16) Synthesis of the core-shell dye prepared in Example 16 (expressed by Chemical Formula 5-16) (A-17) Synthesis of the core-shell dye prepared in Example 17 (expressed by Chemical Formula 5-17) ( A-18) Synthesis of the core-shell dye prepared in Example 18 (expressed by Chemical Formula 5-18) (A-19) Synthesis of the core-shell dye prepared in Example 19 (expressed by Chemical Formula 5-19) (A-20) Core-shell dye prepared in Synthesis Example 20 (expressed by Chemical Formula 5-20) (A-21) Core-shell dye prepared in Synthesis Example 21 (expressed by Chemical Formula 5-21) (A-22) Synthesis Example 22 Core-shell dye prepared (expressed by Chemical Formula 5-22) (A-23) Core-shell dye prepared in Synthesis Example 23 (expressed by Chemical Formula 5-23) (A-24) Core-shell dye prepared in Synthesis Example 24 Shell dye (represented by Chemical Formula 5-24) (A-25) Comparative synthesis of core-shell dye (pigment) prepared in Example 1 (A'-1) CI green pigment 58 (B) Binder resin has 22,000 g/mol The weight average molecular weight of methacrylic acid/benzyl methacrylate copolymer (mixing weight ratio: 15% by weight/85% by weight). (C) Photopolymerizable monomer dipentaerythritol hexaacrylate (D) Photopolymerization initiator (D-1) 1,2-octanedione (D-2) 2-dimethylamino-2-(4-methyl methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (E) solvent (E-1) cyclohexanone (E-2) propylene glycol monomethyl ether Acetate Examples 1 to 24 , Comparative Example 1 and Comparative Example 2

A photosensitive resin composition was prepared by mixing each component of the compositions shown in Table 1 and Table 2. Specifically, the photopolymerization initiator was dissolved in the solvent, the solution was stirred at room temperature for 2 hours, a colorant was added thereto, the mixture was stirred for 30 minutes, a binder resin and a photopolymerizable monomer were added thereto, and The resulting mixture was stirred at room temperature for 2 hours. The solution was filtered three times to remove impurities and prepare a photosensitive resin composition.

[Table 1] (Unit: weight %) Example 1 2 3 4 5 6 7 8 9 10 11 12 13 (A,A') colorant A-1 2 - - - - - - - - - - - - A-2 - 2 - - - - - - - - - - - A-3 - - 2 - - - - - - - - - - A-4 - - - 2 - - - - - - - - - A-5 - - - - 2 - - - - - - - - A-6 - - - - - 2 - - - - - - - A-7 - - - - - - 2 - - - - - - A-8 - - - - - - - 2 - - - - - A-9 - - - - - - - - 2 - - - - A-10 - - - - - - - - - 2 - - - A-11 - - - - - - - - - - 2 - - A-12 - - - - - - - - - - - 2 - A-13 - - - - - - - - - - - - 2 A'-1 - - - - - - - - - - - - - (B) Binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) Photopolymerizable monomer 8 8 8 8 8 8 8 8 8 8 8 8 8 (D) Photopolymerization initiator D-1 1 1 1 1 1 1 1 1 1 1 1 1 1 D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent E-1 40 40 40 40 40 40 40 40 40 40 40 40 40 E-2 45 45 45 45 45 45 45 45 45 45 45 45 45

[Table 2] (Unit: weight %) Example Comparative example 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 1 2 (A,A') colorant A-14 2 - - - - - - - - - - - - A-15 - 2 - - - - - - - - - - - A-16 - - 2 - - - - - - - - - - A-17 - - - 2 - - - - - - - - - A-18 - - - - 2 - - - - - - - - A-19 - - - - - 2 - - - - - - - A-20 - - - - - - 2 - - - - - - A-21 - - - - - - - 2 - - - - - A-22 - - - - - - - - 2 - - - - A-23 - - - - - - - - - 2 - - - A-24 - - - - - - - - - - 2 - - A-25 - - - - - - - - - - - 2 - A'-1 - - - - - - - - - - - - 2 (B) Binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) Photopolymerizable monomer 8 8 8 8 8 8 8 8 8 8 8 8 8 (D) Photopolymerization initiator D-1 1 1 1 1 1 1 1 1 1 1 1 1 1 D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent E-1 40 40 40 40 40 40 40 40 40 40 40 40 40 E-2 45 45 45 45 45 45 45 45 45 45 45 45 45 (Evaluation) Evaluation 1 : Evaluating durability

The photosensitive resin compositions according to Examples 1 to 24, Comparative Example 1 and Comparative Example 2 with a thickness of 1 micron to 3 microns were respectively coated on a 1 mm thick degreased glass substrate and dried on a 90°C hot plate for 2 minutes, Obtain membrane. The film was exposed using a high-pressure mercury lamp with a dominant wavelength of 365 nm and dried in an oven at 200°C for 60 hours, and a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.) measured the color coordinate change and Durability was thus evaluated, and the results are shown in Table 3. Durability evaluation reference Excellent: Color coordinate change is less than 0.003 Good: Color coordinate change is greater than or equal to 0.003 and less than or equal to 0.005 Poor: Color coordinate change is higher than 0.005

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Durability good good good good good Excellent good good good good good Excellent good Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Comparative example 1 Comparative example 2 Durability good good good good Excellent good good good good good Excellent Poor Poor

According to Table 3, the photosensitive resin compositions of Examples 1 to 24 including the core-shell dye according to the embodiment showed increased durability. Evaluation 2 : Evaluate brightness and contrast ratio

The photosensitive resin compositions according to Examples 1 to 24, Comparative Example 1 and Comparative Example 2 with a thickness of 1 micron to 3 microns were respectively coated on a 1 mm thick degreased glass substrate and dried on a 90° C. hot plate for 2 minutes. Form a film. Subsequently, the film was exposed using a high pressure mercury lamp with a dominant wavelength of 365 nm and dried in a forced convection drying oven at 200°C for 5 minutes. The brightness and contrast ratio of the pixel layer were measured using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.), and the results are shown in Table 4.

[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 brightness(%) 67.1 67.3 67.2 67.4 67.2 67.5 67.3 67.2 67.4 67.1 67.3 67.2 67.3 contrast ratio 14700 14900 15100 15200 14900 15300 15200 15100 14900 15100 15200 15100 14900 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Comparative example 1 Comparative example 2 brightness(%) 67.4 67.3 67.5 67.2 67.4 67.3 67.3 67.2 67.3 67.4 67.5 65.9 63.5 contrast ratio 15200 15100 14800 15000 14900 15200 14800 14700 15100 14900 14800 14100 12500

According to Table 4, Examples 1 to 24 including the core-shell dye according to the embodiment showed high brightness and high contrast ratio compared to Comparative Example 1 and Comparative Example 2 not including the core-shell dye.

While the present invention has been described in connection with what are presently considered practical example embodiments, it should be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover the spirit and scope included within the scope of the appended claims. Various modifications and equivalent arrangements within. Therefore, the foregoing embodiments should be understood as illustrative and not in any way limiting the invention.

without.

FIG. 1 is a view illustrating the cage width of the shell represented by Chemical Formula 3-4.

Claims (12)

A photosensitive resin composition, including based on the total amount of the photosensitive resin composition, 0.5% to 20% by weight of (A) colorant, including a dye with a core-shell structure; 0.1% to 30% by weight (B) binder resin; 0.1% to 30% by weight of (C) photopolymerizable compound; (D) photopolymerization initiator; and (E) solvent, wherein the core includes an aromatic cyanine compound, The aromatic cyanine compound is represented by Chemical Formula 4, and the shell is represented by Chemical Formula 3-3 or Chemical Formula 3-4:

Wherein, in Chemical Formula 4, R ⁹ to R ¹² are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl group, [Chemical Formula 3-3]

The photosensitive resin composition according to claim 1, wherein the shell has a cage width of 6.5 angstroms to 7.5 angstroms. The photosensitive resin composition according to claim 1, wherein the core has a length of 1 nm to 3 nm. The photosensitive resin composition according to claim 1, wherein the core has a maximum absorption peak in a wavelength of 530 nanometers to 680 nanometers. The photosensitive resin composition according to claim 1, wherein the aromatic cyanine compound is represented by one of Chemical Formula 4-1 to Chemical Formula 4-6: [Chemical Formula 4-1]

[Chemical formula 4-6]

The photosensitive resin composition according to claim 1, wherein the core-shell structure dye includes the core and the shell with a molar ratio of 1:1. The photosensitive resin composition according to claim 1, wherein the core-shell structure dye is a green dye. The photosensitive resin composition according to claim 1, wherein the colorant further includes a pigment. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition includes 0.1% to 5% by weight of the photopolymerization initiator based on the total amount of the photosensitive resin composition. ; and the balance of the solvent. The photosensitive resin composition as claimed in claim 1, wherein the photosensitive resin composition further includes malonic acid, 3-amino-1,2-propanediol, silane coupling agent, leveling agent, surfactant, Free radical polymerization initiator or a combination thereof, the silane coupling agent includes vinyl or (meth)acryloxy group. A photosensitive resin layer produced using the photosensitive resin composition according to any one of claims 1 to 10. A color filter including the photosensitive resin layer as described in claim 11.

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