Photosensitive resin composition, photosensitive resin layer and color filter

Abstract

The present application provides a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter including the photosensitive resin layer, wherein the photosensitive resin composition includes: (A) a colorant including a dye having a core-shell structure; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the core is an aromatic acid cyanine compound and the shell is represented by Chemical Formula 1. In Chemical Formula 1, each substituent is the same as defined in the specification. The present application can improve the durability of the color filter and have high brightness and high contrast ratio. [Chemical Formula 1]

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0051681 filed on May 2, 2019, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] 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. Background Art

[0004] Among many types of displays, liquid crystal displays have advantages in brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been more widely used in laptop computers, 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 portion including a liquid crystal layer, a thin film transistor, and a capacitor layer are formed. The color filter is formed in a pixel region by sequentially stacking a plurality of pixel portions generally formed of three primary colors in a predetermined order, such as red (R), green (G), and blue (B), to form each pixel, and a black matrix layer is disposed in a predetermined pattern on a transparent substrate to form a boundary between pixels.

[0005] The pigment dispersion method is one of the methods for forming a color filter, and a colored film is provided by repeating a series of processes such as: coating a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix, exposing the formed pattern, removing the non-exposed portion with a solvent, and thermally curing it. 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. The pigment dispersion method is actively used to manufacture LCDs such as mobile phones, laptop computers, monitors, and TVs. However, the photosensitive resin composition used for the color filter of the pigment dispersion method has 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 needed.

[0006] An image sensor is a component used for photography in a portable phone camera or a digital still camera (DSC). Image sensors can be classified into charge-coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors depending on the manufacturing process and application method. A color imaging device for a charge-coupled device image sensor or a complementary metal oxide semiconductor image sensor includes color filters each having a filter segment of a mixed primary color of red, green, and blue, and the colors are separated. The nearest color filter installed in the color imaging device has a pattern size of 2 microns or less, which is 1 / 100 to 1 / 200 of the pattern size of a conventional color filter pattern used for an LCD. Therefore, increased resolution and reduced pattern residues are important factors in determining device performance.

[0007] Color filters manufactured by using a pigment-type photosensitive resin composition have limitations in brightness and contrast ratio due to the size of the pigment particles. In addition, color imaging devices for image sensors require a smaller dispersed particle size for forming fine patterns. In order to meet the requirements, efforts have been made to obtain color filters with improved brightness and contrast ratio by introducing non-particle-forming dyes 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 can be reduced. Summary of the invention

[0008] Embodiments provide a photosensitive resin composition having improved brightness and durability.

[0009] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0010] Another embodiment provides a color filter including a photosensitive resin layer.

[0011] An embodiment provides 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 acid cyanine compound and the shell is represented by Chemical Formula 1.

[0012] [Chemical formula 1]

[0013]

[0014] In Chemical Formula 1,

[0015] 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 a bonding position),

[0016] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0017] The restriction is that R 1 to R 5 Different from hydrogen atoms,

[0018] m is an integer from 1 to 10,

[0019] n is an integer from 0 to 3, and

[0020] L 1 and L 2 and C1 to C10 are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

[0021] The shell can be represented by Chemical Formula 2.

[0022] [Chemical formula 2]

[0023]

[0024] In chemical formula 2,

[0025] 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 a bonding position),

[0026] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0027] The restriction is that R 1 to R 5 are not both hydrogen atoms, and

[0028] n is an integer from 0 to 3.

[0029] The shell may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-3.

[0030] [Chemical formula 2-1]

[0031]

[0032] [Chemical formula 2-2]

[0033]

[0034] [Chemical formula 2-3]

[0035]

[0036] In Chemical Formula 2-1 to Chemical Formula 2-3,

[0037] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0038] R 7 and R 8 are independently 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 a bonding position).

[0039] The shell may have a cage width of 6.5 angstroms to 7.5 angstroms.

[0040] The shell may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-4.

[0041] [Chemical formula 3-1]

[0042]

[0043] [Chemical formula 3-2]

[0044]

[0045] [Chemical formula 3-3]

[0046]

[0047] [Chemical formula 3-4]

[0048]

[0049] The aromatic acid cyanine compound can be represented by Chemical Formula 4.

[0050] [Chemical formula 4]

[0051]

[0052] In chemical formula 4,

[0053] R 9 to R 12and R and R are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl.

[0054] The core may have a length of 1 nanometer to 3 nanometers.

[0055] The core may have a maximum absorption peak in a wavelength of 530 nanometers to 680 nanometers.

[0056] The aromatic acid cyanine compound can be represented by one of Chemical Formula 4-1 to Chemical Formula 4-6.

[0057] [Chemical formula 4-1]

[0058]

[0059] [Chemical formula 4-2]

[0060]

[0061] [Chemical formula 4-3]

[0062]

[0063] [Chemical formula 4-4]

[0064]

[0065] [Chemical formula 4-5]

[0066]

[0067] [Chemical formula 4-6]

[0068]

[0069] The core-shell structured dye may comprise a core and a shell in a molar ratio of 1:1.

[0070] The core-shell structured dye may be a green dye.

[0071] The colorant may further comprise a pigment.

[0072] The photosensitive resin composition may include 0.5 wt % to 20 wt % of a colorant, based on the total amount of the photosensitive resin composition; 0.1 wt % to 30 wt % of a binder resin; 0.1 wt % to 30 wt % of a photopolymerizable compound (monomer); 0.1 wt % to 5 wt % of a photopolymerization initiator; and the remainder a solvent.

[0073] 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, wherein the silane coupling agent includes a vinyl group or a (meth)acryloyloxy group.

[0074] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0075] Another embodiment provides a color filter including a photosensitive resin layer. Other embodiments of the present invention are included in the following detailed description.

[0076] The photosensitive resin composition according to an embodiment may implement a color filter having improved brightness and durability by using a core-shell dye including a shell having a special structure surrounding an aromatic acid cyanine core. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1 is a view showing the cage width of the shell represented by Chemical Formula 3-4. DETAILED DESCRIPTION

[0078] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and is defined by the scope of the claims.

[0079] In the present specification, when a specific definition is not otherwise provided, “substituted” means replacement of at least one hydrogen of a compound by a substituent selected from a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, and combinations thereof.

[0080] In the present specification, when no specific definition is provided otherwise, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" refer to cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene cyclic compounds containing at least one heteroatom of N, O, S or P.

[0081] In the present specification, when a specific definition is not otherwise provided, "(meth)acrylate" means both "acrylate" and "methacrylate".

[0082] In the present specification, when no particular definition is otherwise provided, "combination" means mixing or copolymerization.

[0083] In the present specification, when a definition is not otherwise provided, in a chemical formula, when a chemical bond is not drawn, hydrogen is bonded at a position presumably given.

[0084] In the present specification, when a specific definition is not otherwise provided, "*" indicates a point of bonding to the same or different atoms or chemical formulas.

[0085] The photosensitive resin composition according to an embodiment includes: (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 an aromatic acid cyanine compound and the shell is represented by Chemical Formula 1.

[0086] [Chemical formula 1]

[0087]

[0088] In Chemical Formula 1,

[0089] 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, and * is a bonding position),

[0090] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0091] The restriction is that R 1 to R 5 Different from hydrogen atoms,

[0092] m is an integer from 1 to 10,

[0093] n is an integer from 0 to 3, and

[0094] L 1 and L 2 and C1 to C10 are independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

[0095] In chemical formula 1, L 1 and L 2 may be independently a substituted or unsubstituted C1 to C10 alkylene group. In this case, the solubility is improved and a structure in which a shell surrounds the aromatic acid cyanine compound is easily formed.

[0096] For example, the core-shell dye according to the embodiment includes a non-covalent bond between an oxygen atom of the aromatic acid cyanine-based compound and a hydrogen atom bonded to a nitrogen atom of the shell represented by Chemical Formula 1, that is, a hydrogen bond.

[0097] In general, aromatic acid cyanine compounds are often used as green dyes because they have improved green spectral characteristics and high molar absorption coefficients. However, after manufacturing a color resist with poor durability compared to a pigment, the brightness may decrease during the baking process. In the photosensitive resin composition according to an embodiment, a core-shell structure compound is used as a colorant instead of a conventional aromatic acid cyanine compound, in which the shell represented by Chemical Formula 1 uses an aromatic acid cyanine compound as a core 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 a high contrast ratio.

[0098] Hereinafter, each component is described specifically.

[0099] (A) Colorants

[0100] The photosensitive resin composition according to an embodiment includes a dye of a core-shell structure.

[0101] As described above, in a color filter made of a pigment-type photosensitive resin composition, there are limitations on brightness and contrast ratio due to the pigment particle size. In addition, for application to an image sensor, a resin composition composed of smaller particles is required for forming a fine pattern. 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 a dye. However, dyes have poor durability compared to pigments, and thus there are limitations on improving brightness and contrast ratio.

[0102] However, in the case of a dye used as a colorant in the photosensitive resin composition according to the embodiment, the center of the aromatic acid cyanine compound having excellent green spectrum characteristics and a high molar extinction coefficient is surrounded by the macrocyclic compound represented by Chemical Formula 1, and the durability can be improved more than that of the pigment-type photosensitive resin composition and the dye-type photosensitive resin composition to implement a color filter with brightness and contrast ratio.

[0103] Specifically, the core-shell dye has a structure consisting of an aromatic acid cyanine core and a shell surrounding the core, and the shell of the macrocyclic compound represented by Chemical Formula 1 surrounds the aromatic acid cyanine core to form a coating. Due to this structure, that is, by having a structure in which the aromatic acid 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 a color filter having high brightness and high contrast ratio can be implemented.

[0104] For example, the shell may be represented by Chemical Formula 2.

[0105] [Chemical formula 2]

[0106]

[0107] In chemical formula 2,

[0108] 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, and * is a bonding position),

[0109] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0110] The restriction is that R 1 to R 5 are not both hydrogen atoms, and

[0111] n is an integer from 0 to 3.

[0112] For example, in Chemical Formula 1 and Chemical Formula 2, R 1 can be a hydrogen atom, and R 2 to R 5 may be independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, provided that R 2 to R 5 At least one of the groups is a substituted or unsubstituted C1 to C20 alkyl group.

[0113] For example, in Chemical Formula 1 and Chemical Formula 2, R 1 It 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, and * is a bonding position), R 2 to R 5 are independently hydrogen atoms.

[0114] For example, R 1 It 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, and * is a bonding position), and R 2 to R 5 At least one of the may be a substituted or unsubstituted C1 to C20 alkyl group.

[0115] For example, Chemical Formula 2 can be represented by Chemical Formula 2A.

[0116] [Chemical Formula 2A]

[0117]

[0118] In Chemical Formula 2A,

[0119] 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 bonding position), and

[0120] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0121] For example, the shell may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-3.

[0122] [Chemical formula 2-1]

[0123]

[0124] [Chemical formula 2-2]

[0125]

[0126] [Chemical formula 2-3]

[0127]

[0128] In Chemical Formula 2-1 to Chemical Formula 2-3,

[0129] R 2 to R 5 are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0130] R 7 and R 8 are independently 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 bonding position).

[0131] 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 disclosure refers to the internal distance of the shell, for example, in the shell represented by Chemical Formula 2, the distance between two different phenylene groups that bond two methylene groups (see Figure 1 When the shell has a cage width within the range, a core-shell dye having a structure surrounding an aromatic acid cyanine compound can be obtained, and thus when the core-shell dye is used as a colorant for a photosensitive resin composition, a color filter with improved durability and high brightness can be implemented.

[0132] For example, the shell may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-4, but is not limited thereto.

[0133] [Chemical formula 3-1]

[0134]

[0135] [Chemical formula 3-2]

[0136]

[0137] [Chemical formula 3-3]

[0138]

[0139] [Chemical formula 3-4]

[0140]

[0141] For example, in the core-shell dye, the aromatic acid cyanine compound constituting the core may be represented by Chemical Formula 4.

[0142] [Chemical formula 4]

[0143]

[0144] In chemical formula 4,

[0145] R 9 to R 12 and R and R are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl.

[0146] For example, in Chemical Formula 4, R 9 and R 11 may independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R 10 and R 12 and alkyl, ...

[0147] For example, R 9 and R 11They may independently be "C1 to C20 alkyl which may be substituted by C1 to C10 alkoxy" or "C3 to C20 cycloalkyl which may be substituted by C1 to C10 alkoxy".

[0148] 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 with a C1 to C4 alkyl group.

[0149] The compound represented by Chemical Formula 4 has three types of resonance structures as shown in the following drawings, but in this specification, for convenience, a compound represented by Chemical Formula 4 having one type of resonance structure is shown. In other words, the compound represented by Chemical Formula 4 may have any one type of structure among the three types of resonance structures.

[0150]

[0151] For example, the core (that is, the aromatic acid cyanine compound) may be represented by one of Chemical Formulae 4-1 to 4-6, but is not limited thereto.

[0152] [Chemical formula 4-1]

[0153]

[0154] [Chemical formula 4-2]

[0155]

[0156] [Chemical formula 4-3]

[0157]

[0158] [Chemical formula 4-4]

[0159]

[0160] [Chemical formula 4-5]

[0161]

[0162] [Chemical formula 4-6]

[0163]

[0164] For example, when the compounds represented by Chemical Formula 4-1 to Chemical Formula 4-6, and specifically the compounds represented by Chemical Formula 4-6, are used in a photosensitive resin composition (e.g., as a dye), the solubility to the solvent described later may be greater than or equal to 5, for example, 5 to 10. The solubility may be obtained by the amount (g) of the dye (compound) dissolved in 100 g of the solvent. When the compound (e.g., dye) has a solubility within the range, compatibility and coloring properties with other components in the photosensitive resin composition (that is, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator described later) may be ensured, and precipitation of the dye may be prevented.

[0165] For example, the compounds represented by Chemical Formula 4-1 to Chemical Formula 4-6 may have improved heat resistance, that is, a 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.

[0166] The length of the compound represented by Chemical Formula 4 contained in the core 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 a shell as a 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.

[0167] For example, the core-shell structure compound may have a maximum absorption peak in a wavelength of 530 nm to 680 nm. The core-shell structured dye having spectral characteristics is used as a green dye and thus can provide a photosensitive resin composition for a color filter having high brightness and high contrast ratio.

[0168] For example, the core-shell structure compound may include an aromatic acid cyanine core and a shell in a molar ratio of 1: 1. When the core and the shell are present in the molar ratio, a coating layer (shell) surrounding the aromatic acid cyanine core may be well formed.

[0169] For example, the core-shell structured 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.

[0170] [Chemical formula 5-1]

[0171]

[0172] [Chemical formula 5-2]

[0173]

[0174] [Chemical formula 5-3]

[0175]

[0176] [Chemical formula 5-4]

[0177]

[0178] [Chemical formula 5-5]

[0179]

[0180] [Chemical formula 5-6]

[0181]

[0182] [Chemical formula 5-7]

[0183]

[0184] [Chemical formula 5-8]

[0185]

[0186] [Chemical formula 5-9]

[0187]

[0188] [Chemical formula 5-10]

[0189]

[0190] [Chemical formula 5-11]

[0191]

[0192] [Chemical formula 5-12]

[0193]

[0194] [Chemical formula 5-13]

[0195]

[0196] [Chemical formula 5-14]

[0197]

[0198] [Chemical formula 5-15]

[0199]

[0200] [Chemical formula 5-16]

[0201]

[0202] [Chemical formula 5-17]

[0203]

[0204] [Chemical formula 5-18]

[0205]

[0206] [Chemical formula 5-19]

[0207]

[0208] [Chemical formula 5-20]

[0209]

[0210] [Chemical formula 5-21]

[0211]

[0212] [Chemical formula 5-22]

[0213]

[0214] [Chemical formula 5-23]

[0215]

[0216] [Chemical formula 5-24]

[0217]

[0218] The core-shell dye can be used alone as a green dye and can be mixed with an auxiliary dye.

[0219] The auxiliary dye may be a triarylmethane dye, anthraquinone dye, benzylidene dye, cyanine dye, phthalocyanine dye, azaporphyrin dye, indigo dye, xanthene dye, pyridone azo dye, and the like.

[0220] The core-shell dye may be mixed with a pigment. That is, the colorant may further comprise a pigment.

[0221] The pigment may be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, and the like.

[0222] Examples of red pigments may be CI red pigment 254, CI red pigment 255, CI red pigment 264, CI red pigment 270, CI red pigment 272, CI red pigment 177, CI red pigment 89, and the like. Examples of green pigments may be CI green pigment 7, CI green pigment 36, CI green pigment 58, CI green pigment 59, and the like. Examples of blue pigments may be copper phthalocyanine pigments such as CI blue pigment 15:6, CI blue pigment 15, CI blue pigment 15:1, CI blue pigment 15:2, CI blue pigment 15:3, CI blue pigment 15:4, CI blue pigment 15:5, CI blue pigment 16, and the like. Examples of yellow pigments may be isoindoline-based pigments such as CI yellow pigment 139 and the like; quinoline yellow-based pigments such as CI yellow pigment 138 and the like; nickel complex pigments such as CI yellow pigment 150 and the like. Examples of the black pigment may be aniline black, perylene black, titanium black, carbon black, and the like. The pigment may be used alone or in the form of a mixture of two or more and is not limited thereto.

[0223] The pigment may be contained in the photosensitive resin composition for color filters in the form of a pigment dispersion liquid. The pigment dispersion liquid may be composed of a pigment and a solvent, a dispersant, a dispersing resin, and the like.

[0224] 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 is desirably propylene glycol methyl ether acetate.

[0225] The dispersant helps to uniformly disperse the pigment, and may include a nonionic dispersant, an anionic dispersant, or a cationic dispersant. Specific examples may be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylic acid salt, alkylamide alkylene oxide addition product, alkylamine, and may be used alone or in the form of a mixture of two or more.

[0226] The dispersion resin may be an acryl-based resin including a carboxyl group, and improves the stability of the pigment dispersion and the pattern characteristics of pixels.

[0227] When the core-shell dye and the pigment are mixed, the core-shell dye and the pigment may be mixed at a weight ratio of 1:9 to 9:1, and specifically at a weight ratio of 3:7 to 7:3. When the core-shell dye and the pigment are mixed within the weight ratio range, high brightness and contrast ratio may be obtained while maintaining color characteristics.

[0228] The colorant may be included in an amount of 0.5 to 20 wt % (eg, 1 to 15 wt %) based on the total amount of the photosensitive resin composition. When the colorant is used within the range, high brightness and high contrast ratio at desired color coordinates may be achieved.

[0229] (B) Binder resin

[0230] The binder resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer and a resin including at least one acryl-based repeating unit.

[0231] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl group. Examples of the monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0232] The first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt %, for example, 10 to 40 wt %, based on the total amount of the alkali-soluble resin.

[0233] Examples of the second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl 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, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, and the like; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 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 glycidyl (meth)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 examples of the second ethylenically unsaturated monomer may be used alone or in a mixture of two or more.

[0234] Examples of the binder resin may include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and the examples of the binder resin may be used alone or in a mixture of two or more.

[0235] The binder resin may have a weight average molecular weight of 3,000 g / mol to 150,000 g / mol, for example, 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 range, the composition may have excellent close contact characteristics with the substrate, good physical and chemical characteristics, and appropriate viscosity.

[0236] The binder resin may have an acid value of about 15 to about 60 mg KOH / g, for example about 20 to about 50 mg KOH / g. When the binder resin has an acid value within the range, it may provide excellent pixel resolution.

[0237] The binder resin may be included in an amount of 0.1 wt % to 30 wt % (e.g., 5 wt % to 20 wt %) based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, the composition may have excellent developability and improved cross-linking, and thus have excellent surface flatness when manufactured into a color filter.

[0238] (C) Photopolymerizable monomer

[0239] The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

[0240] The photopolymerizable monomer has an ethylenically unsaturated double bond, and therefore, can cause sufficient polymerization during exposure in a pattern formation process and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

[0241] Specific examples of the photopolymerizable monomer may 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, and bisphenol A di(meth)acrylate. (meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, aldehyde epoxy (meth)acrylate and the like.

[0242] Commercially available examples of reactive unsaturated compounds are as follows. Monofunctional (meth)acrylates may include Aronix (Toagosei Chemistry Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co., Ltd.); (Osaka Organic Chemical Ind., Ltd.) and the like. Examples of the bifunctional (meth)acrylate may include Anix (Toa Synthetic Chemical Industry Co., Ltd.), Kayalade (Nippon Kayaku Co., Ltd.), V-335 (Osaka Organic Chemical Industry Co., Ltd.) and the like. Examples of trifunctional (meth)acrylates may include Anix (Toa Synthetic Chemical Industry Co., Ltd.), Kayalade (Nippon Kayaku Co., Ltd.), (Osaka Yuki Kayaku Kogyo Co. Ltd.) and the like. These may be used alone or in admixture of two or more.

[0243] The photopolymerizable monomers may be treated with anhydrides to improve developability.

[0244] The photopolymerizable monomer may be included in an amount of 0.1 wt % to 30 wt % (eg, 5 wt % to 20 wt %) based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, pattern characteristics and developability may be improved during color filter manufacturing.

[0245] (D) Photopolymerization initiator

[0246] The photopolymerization initiator may include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, and the like.

[0247] Examples of acetophenone compounds may include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0248] Examples of the benzophenone compounds may include benzophenone, benzoyl benzoate, benzoyl methylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 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.

[0249] Examples of the thioxanthone-based compound may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0250] Examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0251] Examples of triazine compounds may include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-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, and 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine. methyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthol)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxyphenylvinyl)-6-triazine and the like.

[0252] Examples of the oxime compound may include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetoxiime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, and the like.

[0253] The photopolymerization initiator may include, in addition to the compounds, carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, fluorene-based compounds, and the like.

[0254] The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt % (e.g., 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, the composition may be sufficiently photopolymerized when exposed during a pattern forming process for preparing a color filter, thereby achieving excellent sensitivity and improving transmittance.

[0255] (E) Solvent

[0256] 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, methylphenyl 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 acetates such as cellosolve methyl acetate, cellosolve ethyl acetate, cellosolve diethyl acetate and the like; carbitols (carbitols) such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ... propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, and the like; aromatic hydrocarbons, such as toluene, xylene, and the like; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butyl ketone, 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; lactic acid alkyl esters, such as methyl lactate, ethyl lactate, and the like; glycolic acid alkyl esters, such as methyl glycolate, ethyl glycolate, butyl glycolate, and the like; analogs; alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate and the like; 3-hydroxyalkyl propionates such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate and the like; 3-alkoxyalkyl propionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and the like; 2-hydroxyalkyl propionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate and the like; 2-alkoxyalkyl propionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate and the like; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionic acid ester, ethyl 2-ethoxy-2-methylpropionic acid ester and the like; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionic acid ester, ethyl 2-ethoxy-2-methylpropionic acid ester and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate and the like; or ketoester compounds such as ethyl pyruvate.In addition, the solvent may be N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, 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.

[0257] Taking into account miscibility, reactivity, and the like, the solvent may include glycol ethers such as ethylene glycol monoethyl ether and the like; ethylene 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 acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.

[0258] The solvent may be included in a balance, and specifically, in an amount of 20 wt % to 90 wt % based on the total amount of the photosensitive resin composition.

[0259] When the solvent is included within the above range, the photosensitive resin composition may have excellent coating characteristics and maintain excellent flatness in a layer having a thickness of 3 micrometers or more.

[0260] (F) Other additives

[0261] The photosensitive resin composition may further contain other additives, such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl or (meth)acryloyloxy group; a leveling agent; a fluorine-based surfactant; a free radical polymerization initiator, so as to prevent stains or spots during coating, to adjust leveling, or to prevent pattern residues due to non-development.

[0262] The photosensitive resin composition may further include an epoxy compound to improve the close contact property with the substrate.

[0263] Examples of the epoxy compound may include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A epoxy compound, an alicyclic epoxy compound, or a combination thereof.

[0264] The amount of additives used can be controlled depending on the desired properties.

[0265] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0266] Another embodiment provides a color filter manufactured using the photosensitive resin composition. The method for manufacturing the color filter is as follows.

[0267] A protective layer (SiN) having a thickness of 500 angstroms to 1500 angstroms is coated on or above the bare glass substrate using an appropriate method such as spin coating, slit coating, and the like. x A photosensitive resin composition for a color filter having a thickness of 3.1 to 3.4 microns is coated on a glass substrate of 100 μm (200 μm). After coating, the composition is irradiated with light to form a pattern required for a color filter. After irradiation with light, the coating is treated with an alkaline developer, and its non-irradiated area can be dissolved, thereby forming a pattern for a color filter. This process is repeated depending on the number of desired R, G, and B colors, thereby manufacturing a color filter having a desired pattern.

[0268] 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.

[0269] Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be interpreted as limiting the scope of the present invention in any sense.

[0270] (Preparation of single molecule compounds)

[0271] (Preparation Example 1: Preparation of Intermediate A)

[0272]

[0273] Aniline (10 mol), 4-bromotoluene (10 mol), Pd2(dba)3 (0.1 mol) and Xphos (0.1 mol) 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 an organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain intermediate A.

[0274] (Preparation Example 2: Preparation of Intermediate B-1)

[0275]

[0276] 2,4-dimethyldiphenylamine (10 mol), 1,2-epoxyhexane (12 mol) and sodium hydride (12 mol) 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 an organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate B-1.

[0277] (Preparation Example 3: Preparation of Intermediate B-2)

[0278]

[0279] Intermediate B-2 was obtained according to the same method as Preparation Example 2, except that 1,2-butylene oxide was used instead of 1,2-hexylene oxide.

[0280] (Preparation Example 4: Preparation of Intermediate B-3)

[0281]

[0282] 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.

[0283] (Preparation Example 5: Preparation of Intermediate B-4)

[0284]

[0285] 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.

[0286] (Preparation Example 6: Preparation of Intermediate C-1)

[0287]

[0288] Intermediate B-1 (10 mmol), iodomethane (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.

[0289] (Preparation Example 7: Preparation of Intermediate C-2)

[0290]

[0291] A 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 iodomethane.

[0292] (Preparation Example 8: Preparation of Intermediate C-3)

[0293]

[0294] A 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.

[0295] (Preparation Example 9: Preparation of Intermediate C-4)

[0296]

[0297] A 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.

[0298] (Preparation Example 10: Preparation of Intermediate C-5)

[0299]

[0300] A 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.

[0301] (Preparation Example 11: Preparation of Intermediate C-6)

[0302]

[0303] A 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 iodomethane.

[0304] (Preparation Example 12: Preparation of Chemical Formula 4-1)

[0305]

[0306] 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 by Dean-Stark distillation equipment. 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.

[0307] (Preparation Example 13: Preparation of Chemical Formula 4-2)

[0308] 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.

[0309] (Preparation Example 14: Preparation of Chemical Formula 4-3)

[0310] 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.

[0311] (Preparation Example 15: Preparation of Chemical Formula 4-4)

[0312] 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.

[0313] (Preparation Example 16: Preparation of Chemical Formula 4-5)

[0314] 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.

[0315] (Preparation Example 17: Preparation of Chemical Formula 4-6)

[0316] 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.

[0317] (Preparation of Core-Shell Dyes)

[0318] (Synthesis Example 1: Synthesis Chemical Formula 5-1)

[0319]

[0320] 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-pyridinedicarbonyl dichloride (20 mmol) and (2,3,5,6-tetramethyl-1,4-phenylene)dimethylamine (20 mmol) were dissolved in 60 ml of chloroform and added simultaneously dropwise 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 5-1.

[0321] Maldi-tof MS: 1346.75m / z

[0322] (Synthesis Example 2: Synthesis Chemical Formula 5-2)

[0323] A 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.

[0324] Maldi-tof MS: 1402.82m / z

[0325] (Synthesis Example 3: Synthesis Chemical Formula 5-3)

[0326] A 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.

[0327] Maldi-tof MS: 1290.60m / z

[0328] (Synthesis Example 4: Synthesis Chemical Formula 5-4)

[0329] A 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.

[0330] Maldi-tof MS: 1318.72m / z

[0331] (Synthesis Example 5: Synthesis Chemical Formula 5-5)

[0332] A 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.

[0333] Maldi-tof MS: 1342.72m / z

[0334] (Synthesis Example 6: Synthesis Chemical Formula 5-6)

[0335] 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.

[0336] Maldi-tof MS: 1538.94m / z

[0337] (Synthesis Example 7: Synthesis Chemical Formula 5-7)

[0338]

[0339] 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-pyridinedicarbonyl dichloride (20 mmol) and (2-methyl-1,4-phenylene) dimethylamine (20 mmol) were dissolved in 60 ml of chloroform and added dropwise 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.

[0340] Maldi-tof MS: 1262.66m / z

[0341] (Synthesis Example 8: Synthesis Chemical Formula 5-8)

[0342] 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.

[0343] Maldi-tof MS: 1318.72m / z

[0344] (Synthesis Example 9: Synthesis Chemical Formula 5-9)

[0345] A 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.

[0346] Maldi-tof MS: 1206.59m / z

[0347] (Synthesis Example 10: Synthesis Chemical Formula 5-10)

[0348] A 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.

[0349] Maldi-tof MS: 1234.63m / z

[0350] (Synthesis Example 11: Synthesis Chemical Formula 5-11)

[0351] A 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.

[0352] Maldi-tof MS: 1258.63m / z

[0353] (Synthesis Example 12: Synthesis Chemical Formula 5-12)

[0354] 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.

[0355] Maldi-tof MS: 1454.84m / z

[0356] (Synthesis Example 13: Synthesis Chemical Formula 5-13)

[0357]

[0358] 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-dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 ml of chloroform and added dropwise 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 5-13.

[0359] Maldi-tof MS: 1370.60m / z

[0360] (Synthesis Example 14: Synthesis Chemical Formula 5-14)

[0361] A 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.

[0362] Maldi-tof MS: 1426.66m / z

[0363] (Synthesis Example 15: Synthesis Chemical Formula 5-15)

[0364] A 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.

[0365] Maldi-tof MS: 1314.54m / z

[0366] (Synthesis Example 16: Synthesis Chemical Formula 5-16)

[0367] A 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.

[0368] Maldi-tof MS: 1342.57m / z

[0369] (Synthesis Example 17: Synthesis Chemical Formula 5-17)

[0370] A 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.

[0371] Maldi-tof MS: 1366.57m / z

[0372] (Synthesis Example 18: Synthesis Chemical Formula 5-18)

[0373] A 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.

[0374] Maldi-tof MS: 1562.79m / z

[0375] (Synthesis Example 19: Synthesis Chemical Formula 5-19)

[0376]

[0377] 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-dicarbonyl dichloride (20 mmol) and p-xylenediamine (20 mmol) were dissolved in 60 ml of chloroform and added dropwise 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 5-19.

[0378] Maldi-tof MS: 1490.87m / z

[0379] (Synthesis Example 20: Synthesis Chemical Formula 5-20)

[0380] A 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.

[0381] Maldi-tof MS: 1546.93m / z

[0382] (Synthesis Example 21: Synthesis Chemical Formula 5-21)

[0383] A 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.

[0384] Maldi-tof MS: 1434.80m / z

[0385] (Synthesis Example 22: Synthesis Chemical Formula 5-22)

[0386] A 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.

[0387] Maldi-tof MS: 1462.83m / z

[0388] (Synthesis Example 23: Synthesis Chemical Formula 5-23)

[0389] A 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.

[0390] Maldi-tof MS: 1486.83m / z

[0391] (Synthesis Example 24: Synthesis Chemical Formula 5-24)

[0392] A 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.

[0393] Maldi-tof MS: 1683.05m / z

[0394] (Comparative Synthesis Example 1)

[0395]

[0396] 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-pyridine dicarbonyl dichloride (20 mmol) and p-xylene diamine (20 mmol) were dissolved in 60 ml of chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a core-shell structure compound.

[0397] (Preparation of photosensitive resin composition)

[0398] The photosensitive resin composition was prepared using the following components.

[0399] (A) Colorants

[0400] (dye)

[0401] (A-1) Synthesis of the core-shell dye prepared in Example 1 (represented by Chemical Formula 5-1)

[0402] (A-2) Synthesis of the core-shell dye prepared in Example 2 (represented by Chemical Formula 5-2)

[0403] (A-3) Synthesis of the core-shell dye prepared in Example 3 (represented by Chemical Formula 5-3)

[0404] (A-4) Synthesis of the core-shell dye prepared in Example 4 (represented by Chemical Formula 5-4)

[0405] (A-5) Synthesis of the core-shell dye prepared in Example 5 (represented by Chemical Formula 5-5)

[0406] (A-6) Synthesis of the core-shell dye prepared in Example 6 (represented by Chemical Formula 5-6)

[0407] (A-7) Synthesis of the core-shell dye prepared in Example 7 (represented by Chemical Formula 5-7)

[0408] (A-8) The core-shell dye prepared in Synthesis Example 8 (represented by Chemical Formula 5-8)

[0409] (A-9) The core-shell dye prepared in Synthesis Example 9 (represented by Chemical Formula 5-9)

[0410] (A-10) The core-shell dye prepared in Synthesis Example 10 (represented by Chemical Formula 5-10)

[0411] (A-11) The core-shell dye prepared in Synthesis Example 11 (represented by Chemical Formula 5-11)

[0412] (A-12) The core-shell dye prepared in Synthesis Example 12 (represented by Chemical Formula 5-12)

[0413] (A-13) The core-shell dye prepared in Synthesis Example 13 (represented by Chemical Formula 5-13)

[0414] (A-14) The core-shell dye prepared in Synthesis Example 14 (represented by Chemical Formula 5-14)

[0415] (A-15) The core-shell dye prepared in Synthesis Example 15 (represented by Chemical Formula 5-15)

[0416] (A-16) The core-shell dye prepared in Synthesis Example 16 (represented by Chemical Formula 5-16)

[0417] (A-17) The core-shell dye prepared in Synthesis Example 17 (represented by Chemical Formula 5-17)

[0418] (A-18) The core-shell dye prepared in Synthesis Example 18 (represented by Chemical Formula 5-18)

[0419] (A-19) The core-shell dye prepared in Synthesis Example 19 (represented by Chemical Formula 5-19)

[0420] (A-20) The core-shell dye prepared in Synthesis Example 20 (represented by Chemical Formula 5-20)

[0421] (A-21) The core-shell dye prepared in Synthesis Example 21 (represented by Chemical Formula 5-21)

[0422] (A-22) The core-shell dye prepared in Synthesis Example 22 (represented by Chemical Formula 5-22)

[0423] (A-23) The core-shell dye prepared in Synthesis Example 23 (represented by Chemical Formula 5-23)

[0424] (A-24) The core-shell dye prepared in Synthesis Example 24 (represented by Chemical Formula 5-24)

[0425] (A-25) Comparative Synthesis of Core-Shell Dyes Prepared in Example 1

[0426] (pigment)

[0427] (A'-1)CI Green Pigment 58

[0428] (B) Binder resin

[0429] A methacrylic acid / benzyl methacrylate copolymer (mixing weight ratio: 15 wt % / 85 wt %) having a weight average molecular weight of 22,000 g / mol.

[0430] (C) Photopolymerizable monomer

[0431] Dipentaerythritol hexaacrylate

[0432] (D) Photopolymerization initiator

[0433] (D-1) 1,2-Octanedione

[0434] (D-2) 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

[0435] (E) Solvent

[0436] (E-1) Cyclohexanone

[0437] (E-2) Propylene glycol monomethyl ether acetate

[0438] Examples 1 to 24, Comparative Examples 1 and 2

[0439] The photosensitive resin composition was prepared by mixing each component in the composition shown in Table 1 and Table 2. Specifically, a photopolymerization initiator was dissolved in a 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 obtained mixture was stirred at room temperature for 2 hours. The solution was filtered three times to remove impurities and a photosensitive resin composition was prepared.

[0440] [Table 1]

[0441] (Unit: weight %)

[0442]

[0443] [Table 2]

[0444] (Unit: weight %)

[0445]

[0446] (Evaluate)

[0447] Assessment 1: Assessing durability

[0448] The photosensitive resin compositions according to Examples 1 to 24, Comparative Examples 1 and 2 were coated on 1 mm thick degreased glass substrates with a thickness of 1 μm to 3 μm, respectively, and dried on a 90° C. hot plate for 2 minutes to obtain films. The films were exposed using a high pressure mercury lamp having 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.) was used to measure the color coordinate change and thereby evaluate the durability, and the results are shown in Table 3.

[0449] Durability Evaluation Reference

[0450] Excellent: Color coordinate change is less than 0.003

[0451] Good: Color coordinate change is greater than or equal to 0.003 and less than or equal to 0.005

[0452] Poor: Color coordinate change is greater than 0.005

[0453] [Table 3]

[0454]

[0455] 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.

[0456] Evaluation 2: Evaluating brightness and contrast ratio

[0457] The photosensitive resin compositions according to Examples 1 to 24, Comparative Examples 1 and 2 were coated with 1 μm to 3 μm thick on a 1 mm thick degreased glass substrate and dried on a 90° C. hot plate for 2 minutes to form a film. Subsequently, the film was exposed to a high pressure mercury lamp having a main 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.

[0458] [Table 4]

[0459]

[0460] 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 with Comparative Examples 1 and 2 not including the core-shell dye.

[0461] Although the present invention has been described in conjunction with what are presently considered to be practical example embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, the present invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the foregoing embodiments should be understood as exemplary and not limiting the present invention in any way.

Claims

1. A photosensitive resin composition comprising (A) colorants, including core-shell dyes; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; as well as (E) a solvent, wherein the core comprises an aromatic acid cyanine compound, wherein the aromatic acid cyanine compound is represented by Chemical Formula 4, and The shell is represented by one of Chemical Formula 3-1 to Chemical Formula 3-4: [Chemical formula 4] Among them, in chemical formula 4, R 9 and R 11 are independently C1 to C20 alkyl groups which may be substituted by C1 to C10 alkoxy groups or C3 to C20 cycloalkyl groups which may be substituted by C1 to C10 alkoxy groups, R 10 and R 12 are independently substituted or unsubstituted C6 to C20 aryl, [Chemical formula 3-1] [Chemical formula 3-2] [Chemical formula 3-3] [Chemical formula 3-4] 2 . The photosensitive resin composition according to claim 1 , wherein the shell has a cage width of 6.5 angstroms to 7.5 angstroms. 3 . The photosensitive resin composition according to claim 1 , wherein the core has a length of 1 nm to 3 nm. 4 . The photosensitive resin composition according to claim 1 , wherein the core has a maximum absorption peak in a wavelength range of 530 nm to 680 nm.

5. The photosensitive resin composition according to claim 1, wherein the aromatic acid cyanine compound is 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] 6 . The photosensitive resin composition according to claim 1 , wherein the core-shell structured dye comprises the core and the shell in a molar ratio of 1:

1. 7 . The photosensitive resin composition according to claim 1 , wherein the core-shell structured dye is a green dye. 8 . The photosensitive resin composition according to claim 1 , wherein the colorant further comprises a pigment.

9. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises Based on the total amount of the photosensitive resin composition, 0.5 to 20 wt % of said colorant; 0.1 wt % to 30 wt % of said binder resin; 0.1 wt % to 30 wt % of the photopolymerizable compound; 0.1 wt % to 5 wt % of the photopolymerization initiator; and The balance is the solvent.

10. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises 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 comprises a vinyl group or a (meth)acryloyloxy group.

11. A photosensitive resin layer manufactured using the photosensitive resin composition according to any one of claims 1 to 10. 12 . A color filter comprising the photosensitive resin layer according to claim 11 .

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