WO2018043829A1

WO2018043829A1 - Novel compound, core-shell dye, photosensitive resin composition comprising same, and color filter

Info

Publication number: WO2018043829A1
Application number: PCT/KR2016/013795
Authority: WO
Inventors: 서혜원; 박채원; 신명엽; 신선웅; 정의수; 최규범
Original assignee: 삼성에스디아이 주식회사
Priority date: 2016-08-29
Filing date: 2016-11-28
Publication date: 2018-03-08
Also published as: KR20180024290A; JP6894500B2; KR102028641B1; CN109689621B; JP2019532918A; CN109689621A; TWI652253B; TW201806929A

Abstract

Provided are a compound represented by a specific formula, a core-shell dye comprising a core comprising the compound and a shell enclosing the core, a photosensitive resin composition comprising the core-shell dye, and a color filter manufactured using the photosensitive resin composition.

Description

【Specification】

[Name of invention]

Novel compounds, core-shell dyes, photosensitive resin compositions and color filters comprising the same

Technical Field

The present disclosure relates to a novel compound, a core-shell dye, a photosensitive resin composition comprising the same, and a color filter manufactured using the same. Background Art

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent integration, and is widely used for notebook computers, monitors, and TV images. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and a πΌ pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer, and an upper substrate on which a πΌ pixel electrode is formed. The color filter comprises a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between pixels, and a plurality of colors, typically red (R), green (G), blue (B) to form each pixel. ) Has a structure in which the pixel portions arranged in the predetermined order in the three primary colors are stacked one by one.

The pigment dispersion method, which is a method of implementing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposes a pattern of a form to be formed, and then removes a non-exposed portion with a solvent. It is a method in which a colored thin film is formed by repeating a series of processes of thermosetting. The coloring photosensitive resin composition used for manufacturing the color filter by the pigment dispersion method generally consists of alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, an epoxy resin, a solvent, other additives, etc. The pigment dispersion method is actively used to manufacture LCDs of mobile phones, notebook computers, monitors, TVs and the like. However, recently, in the photosensitive resin composition for color filters using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also improved performance are required. Especially high color gamut In addition, the characteristics of high brightness and high contrast ratio are urgently required.

The image sensor refers to a component of an image pickup device that generates an image from a mobile phone camera or a digital still camera (DSC). The image sensor is largely complementary to a solid-state charge coupled device (CCD) image sensor according to its manufacturing process and usage. It may be classified as a complementary metal oxide semiconductor (CMOS) image sensor. The color image pickup device used in the solid-state image pickup device or the complementary metal oxide semiconductor includes a color filter having a filter segment of red, green, and blue addition and mixing primary colors on the light receiving device ( It is common to install color filters separately and to separate the colors. Recently, the size of a color filter mounted on such a color image pickup device is 2 μιη or less, which is 1/100 to 1/200 times that of a conventional color filter pattern for LCDs. Accordingly, the increase in resolution and the reduction of residues are important factors that determine the performance of the device.

In the color filter made of the pigment-type photosensitive resin composition, there exists a brightness, contrast ratio, and limit derived from the pigment particle size. In addition, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required for forming a fine pattern. Buung to these needs, by introducing a dye that does not form the particles instead of the pigment to prepare a ^{"photosensitive} resin composition suitable to the dye is an attempt to implement a color filter to improve the brightness and contrast ratio. However, in the case of the dye, the degradation of the luminance due to the deterioration of durability, such as light and heat resistance compared to the pigment.

[Detailed Description of the Invention]

[Technical problem]

One embodiment is to provide novel compounds with excellent brightness and contrast ratio.

Another embodiment is to provide a core-shell dye comprising the novel compound.

Another embodiment is to provide a photosensitive resin composition comprising the novel compound or core-shell dye.

Another embodiment is to provide a color filter manufactured using the photosensitive resin composition. Technical Solution

An embodiment provides a compound represented by the following formula (1).

One]

In Chemical Formula 1,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group,

R ³ and R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

R ¹ and R ² may be each independently represented by the following Formula (2) or (3).

In Additive Formula 2 and Formula 3,

A is a C3 to C20 cycloalkane ring or a benzene ring,

L ³ is a substituted or unsubstituted C1 to C10 alkylene group,

R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. In Formula 1, R ³ and R ⁴ are each independently substituted or unsubstituted C1 It may be a C6 to C20 aryl group unsubstituted or substituted with a CIO alkyl group or a CI to CIO alkyl group.

The compound represented by Chemical Formula 1 may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-8.

1_1]

1-4]

Another embodiment includes a core comprising a compound represented by Formula 1; And a shell surrounding the shell. The cell may be represented by the following Chemical Formula 4 or Chemical Formula 5.

In Chemical Formulas 4 and 5,

L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

L ^a to L ^d may be each independently a substituted or unsubstituted C1 to C10 alkylene group.

The cell may be represented by the following Chemical Formula 4-1 or Chemical Formula 5-1.

[Formula 4-1]

[Formula 5-1]

The cage width of the shell may be 6.5 A to 5 A.

The core may have a length of 1 nm to 3 nm.

The core may have a maximum absorption peak at wavelengths of 530 nm to 680 nm.

The core-shell dye may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21.

[Formula 11]

The core-shell dye may comprise the core and the shell in a molar ratio of 1: 1.

The core-shell dye may be a green dye.

Another embodiment provides a photosensitive resin composition comprising the compound or the core-shell dye.

The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further include a pigment.

The photosensitive resin composition, for a total amount of photosensitive resin composition, the compound or cores - ¾ dye 0.5 ^{^0/0} to 10 parts by weight / _0; The binder resin 0.1 ^_0/0 to 30 parts by weight ⁰ / .; The photopolymerizable monomer 0.1% by weight to 30 parts by weight ^_0/0; 0.1 wt% to 5 wt% of the photopolymerization initiator; and the balance of the solvent. The photosensitive resin composition may be malonic acid, 3-amino-1,2-propanediol, vinyl group, or

A silane coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof containing a (meth) acryloxy group may be further included.

Another embodiment provides a color filter manufactured using the photosensitive resin composition. _And other specific details of the embodiments of the invention are included in the following description.

【Effects of the Invention]

By using the compound or the core-shell dye according to one embodiment, it is possible to implement a color filter having excellent brightness and contrast ratio.

[Brief Description of Drawings]

1 is a view showing the cage width (cage width) of the shell represented by the formula (5-1).

[Best form for implementation of the invention]

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, at least one hydrogen atom of the compound "substituted" 'is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, Imino, azido, amidino, hydrazino, hydrazono, carbonyl, carbamyl, thiol, ester, ether, carboxyl or salts thereof, sulfonic acid or salts thereof, phosphoric acid or its Salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocyclo Alkyl group, C2 to C20

Substituted with a substituent of a heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group or a combination thereof.

Unless otherwise specified in the specification, a "heterocycloalkyl group",

"Heterocycloalkenyl group", "heterocycloalkynyl group", and

"Heterocycloalkylene group" means that at least one hetero atom of _N , ₀ , s or p is present in a ring compound of cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene, respectively. Unless stated otherwise in the present specification, "(meth) acrylate"

It means that both "acrylate" and "methacrylate" are possible.

Unless otherwise specified in this specification, "combination" means mixed or copolymerized.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at the position where the chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

Also, unless stated otherwise in the present specification, "*" means a moiety connected to the same or different atoms or formulas. Compounds according to embodiments are represented by the following Formula 1.

In Chemical Formula 1,

L ¹ and L ² are each independently substituted or unsubstituted C1 to C20

An alkylene group,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

The compound represented by Chemical Formula 1 may be used as a green dye as a compound having excellent green spectroscopic properties and high molar extinction coefficient. However, after the color resist is manufactured with an inferior durability compared to the pigment, a decrease in luminance may occur during the baking process. The compound according to one embodiment may have a substituent including a urethane linking group, thereby improving durability, and thus, having high brightness and high contrast ratio. Color filters can be implemented.

In Formula 1, R ¹ and R ² may be each independently represented by Formula 2 or Formula 3.

3]

In Chemical Formulas 2 and 3,

A is a C3 to C20 cycloalkane ring or a benzene ring

L ³ is a substituted or unsubstituted C1 to C10 alkylene group,

R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

For example, R ¹ and R ² may each independently be a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a C1 to C10 alkyl group including a substituted or unsubstituted acrylate group. have. For example, the C3 to C10 cycloalkyl group may be a cyclopentyl group, a cyclonuclear group, a cycloheptyl group, and the like, but is not limited thereto.

In Formula 1, R ³ and R ⁴ may each independently be a substituted or unsubstituted C1 to C10 alkyl group or a C6 to C20 aryl group unsubstituted or substituted with a C1 to C10 alkyl group.

When the compound represented by Chemical Formula 1 is used in the photosensitive resin composition (for example, as a dye), solubility in a solvent to be described later may be 5 or more, such as 5 to 10. The solubility can be obtained by the amount (g) of the dye (compound) dissolved in 100 g of the solvent. When the solubility of the compound (such as a dye) is within the above range, it is possible to ensure compatibility and coloring power with other components in the photosensitive resin composition, that is, the binder resin, the photopolymerizable monomer, and the photopolymerization initiator, which will be described later. Can be prevented.

The compound represented by Chemical Formula 1 may have excellent heat resistance. In other words,, The pyrolysis temperature, as measured by a thermogravimetric analyzer (TGA), may be ^at least 200 ^° C, such as from 200 ^° C to 300 ^° C.

The compound represented by Chemical Formula 1 has three resonance structures, as shown in the following scheme, but for the sake of convenience, the compound represented by Chemical Formula 1 may be represented by only one resonance structure. That is, the compound represented by Chemical Formula 1 may be represented by any one of three resonance structures.

3

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

Core-shell dye according to another embodiment may have a structure consisting of a core and a shell surrounding the core. The core includes a compound represented by Chemical Formula 1. Specifically, the shell may be a macrocyclic compound, the shell may form a coating layer surrounding the compound represented by the formula (1). In one embodiment, the shell corresponding to the macrocyclic compound has a structure surrounding the compound represented by Chemical Formula 1, that is, the compound represented by Chemical Formula 1 exists inside the macrocyclic ring, It is possible to improve the durability of the core-shell dye, thereby realizing a high brightness and high contrast color filter.

The compound included in the core or constituting the core is represented by Chemical Formula 1: The length of the compound may be 1 nm to 3 nm, such as 1.5 nm to 2 nm. When the compound represented by Formula 1 has a length within the above range, a core-shell dye having a structure of a core and a shell surrounding the compound may be easily formed. In other words, as the compound represented by Chemical Formula 1 has a length within the range, the shell, which is the macrocyclic compound, may be obtained in a structure surrounding the compound represented by Chemical Formula 1. In the case of using other compounds that do not correspond to the length of the above range, it is difficult to expect the improvement of durability due to the difficulty of forming a structure surrounding the compound serving as the core.

Formula 1 contained in the core or constituting the core The compound represented may have a maximum absorption peak at wavelengths of 530 nm to 680 nm. Chemical formula having the above spectral characteristics _. By using the core-shell dye which used the compound represented by 1 as a core as a green dye, for example, the photosensitive resin composition for color filters which has high brightness and high contrast ratio can be obtained.

The shell surrounding the core including the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 4 or Chemical Formula 5.

In Chemical Formulas 4 and 5

L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 halkylene group.

In Formula 2 or Formula 3, L ^a to L ^d may be each independently a substituted or unsubstituted C1 to C10 alkylene group. In this case, it is excellent in solubility and it is easy to form the structure in which a shell surrounds the core containing the compound represented by the said Formula (1).

For example ^! In one embodiment, the core-shell dye is a non-covalent bond, ie, a hydrogen bond, between an oxygen atom of a compound represented by Formula 1 and a hydrogen atom bonded to a nitrogen atom of a shell represented by Formula 4 or Formula 5 It may include.

The shell may be represented by, for example, the formula 4-1 or 5-1.

The cage width of the shell may be 6.5 A to 7.5 A, and the volume of the shell may be 10 A to 16 A. As used herein, the cage width refers to a shell internal distance, such as a distance between two different phenylene groups in which a methylene group is connected to both sides in a shell represented by Formula 4-1 or Formula 5-1. (See Figure 1). When the shell has a cage width within the above range, it is possible to obtain a core-shell dye having a structure surrounding the core containing the ash: compound represented by the formula (1), whereby the core-shell dye is a photosensitive resin When added to the composition it is possible to implement a color filter having excellent durability and high brightness. The core-shell dye may include a core including the compound represented by Chemical Formula 1 and the shell in a molar ratio of 1: 1. When the core and the shell are present in a molar ratio, a coating layer (shell) surrounding the core including the compound represented by Chemical Formula 1 may be well formed.

For example, the core-shell dye may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21, but is not limited thereto.

[Formula 8]

[Formula 12]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 20]

^^

The core-shell dye may be used alone as a green dye, or may be used in combination with a color dye.

Examples of the dye include triaryl methane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azapopyrine dyes, indigo dyes, and xanthene dyes.

The core-shell dyes may also be used in combination with pigments.

As the pigment, a red pigment, a green pigment, a blue pigment, a yellow pigment, or a dark pigment may be used.

Examples of the red pigment include CI. Red pigment 254, and the like can be mentioned CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 177, CI Pigment Red ^'89. Examples of the green pigment include CI green pigment 36, CI green pigment 7, I. green pigment 58 and the like. Examples of the blue pigment include CI blue pigment 15: 6, CI blue pigment 15, CL blue pigment 15: 1, CI blue pigment 15: 2, CI blue pigment 15: 3, CI blue pigment 15: 4, CI blue pigment 15 Copper phthalocyanine pigments, such as: 5 and CL blue pigment 16, are mentioned. Examples of the yellow pigment include isoindolin-based pigments such as CL yellow pigment 139, CI yellow pigment 138, and the like.

Quinophthalone pigments, C.I. Nickel complex pigments such as yellow pigment 150 and the like. Examples of the dark pigment include aniline black, perylene black, titanium black, carbon black and the like. The pigments may be used alone or in combination of two or more thereof, and are not limited to these examples.

The pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion. Such a pigment dispersion may be composed of the pigment, a solvent, a dispersant, a dispersion resin, and the like. The solvent may be ethylene glycol acetate, ethyl salosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol,

Cyclonucanonone, propylene glycol methyl ether, and the like can be used, and among these, propylene glycol methyl ether acetate can be used.

The dispersant helps to uniformly disperse the pigment in the dispersion, it can be used both nonionic, anionic or cationic dispersant. Specifically polyalkylene glycols or esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohols _. Alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkyl ^' amide alkylene oxide adducts, alkyl amines and the like can be used, and these can be used alone or in combination of two or more thereof.

The dispersion resin may use an acrylic resin including a carboxyl group, which may not only improve the stability of the pigment dispersion, but also improve the pattern of the pixel.

When the core-shell dye and the pigment are used in combination, they may be used in a weight ratio of 1: 9 to 9: 1, specifically, in a weight ratio of 3: 7 to 7: 3. When mixed in the weight ratio range, it may have a high brightness and contrast ratio while maintaining color characteristics.

According to another embodiment, the compound represented by Formula 1 or the photosensitive resin composition comprising the core-shell dye is provided

The photosensitive resin composition comprises (A) a colorant - (compound of the formula ^(1), or the core-shell dyes), (B) a binder resin, (C) photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a solvent It may include.

Each component is demonstrated concretely below.

(A) colorant

The colorant may include the compound represented by Chemical Formula 1 and / or the core-shell dye, and the compound represented by Chemical Formula 1 and / or the core-shell dye has been described above.

The colorant is a compound represented by Formula 1 and / or the core-shell In addition to the dye may further comprise a pigment, which has been described above. The formula compound and / or the core is represented by the first-shell dyes the color filter "^ with respect to the photosensitive resin composition the total amount of 0.5 ^_0/0 to 10% by ^weight," e.g. 0.5 ^_0/0 to 5 parts by weight ^_0/0 When the core-shell dye is used within the above range, high luminance and contrast ratios may be expressed at a desired color coordinate.

(B) binder resin

The binder resin is a copolymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.

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

The first ethylenically unsaturated monomer may comprise from 5 parts by weight ^_0/0 to 50% by weight relative to the total amount of the alkali-soluble resin, for example 10% to 40% by weight.

The C2-ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinylluene, and vinylbenzylmethyl ether; Methyl (meth) acrylate,

Ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate,

Unsaturated carboxylic ester compounds such as benzyl (meth) acrylate, cyclonuclear chamber (meth) acrylate, and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compound of vinyl acetate, vinyl benzoate; Vinyl cyanide compounds such as unsaturated carboxylic acid glycidyl ester compound (meth) acrylonitrile such as glycidyl (meth) acrylate; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the binder resin 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 is not limited thereto. These may be used alone or in combination of two or more thereof.

The weight average molecular weight of the binder resin may be 3,000 g / mol to 150,000 g / mol, such as 5,000 g / mol to 50,000 g / mol, such as 20,000 g / mol to 30,000 g / mol ᅳ the weight average molecular weight of the binder resin In the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

The acid value of the binder resin may be 15 mgKOH / g to 60 mgKOH / g, such as 20 mgKOH / g to 50 mgKOH / g. If the acid value of the binder resin is excellent in the above range, the resolution of the pixel can be obtained.

The binder resin may be contained at 0.1 weight ⁰ /. To 30 parts by weight ^_0/0, for example 5% by weight to 20% by weight relative to the total photosensitive resin composition. In the case where the binder resin is included in the above range, the developability and the crosslinkability of the color filter may be improved to obtain excellent surface smoothness.

(C) photopolymerizable monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may form a polymerized layer during exposure in the pattern forming process, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable monomer, 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-nucleic acid diol

Di (meth) acrylate, bisphenol A di (meth) acrylate, di (meth) acrylate, pentaerythritol, tri (meth) acrylate, pentaerythritol, tetra (meth) acrylate, penta Nutri (meta) acrylate, Dipentaerythritol di (meth) acrylate, dipentaerythritol

Tri (meth) acrylate, penta (meth) acrylate for dipentaerythr,

The dipentaerythride is nucleated (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylol propane

Tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate,

Novolak epoxy (meth) acrylate etc. are mentioned.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include, but are not limited to, Aronix M-101 ®, M-1 1 1 ®, M-1 14 ® by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayak Co., Ltd. KAYARAD TC-1 1 OS®, TC-120S®, etc .; And V-158® and V-231 1 ® by Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the difunctional ester of (meth) acrylic acid include, but are not limited to, Aronix M-210®, M-240®, M-6200®, manufactured by Toagosei Kagaku Kogyo Co., Ltd .; KAYARAD HDDA® from Nihon Kayak Co., Ltd., HX-220® R-604®, etc .; The V-260®, V-312®, and V-335 HP® of Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309®, Copper M-400®, Copper M-405®, Copper M-450®, Copper, manufactured by Toagosei Chemical Industries, Ltd. M-7100®, M-8030®, M-8060®, etc .; KAYARAD TMPTA®, Copper DPCA-20®, Copper -30®, Copper -60®, Copper -120®, etc. from Nihon Kayak Co., Ltd .; And V-295®, copper -300®, copper -360®, copper -GPT®, copper -3PA®, and copper -400® from Osaka Yuki Kayaku High School Co., Ltd. These products may be used alone or in combination of two or more.

The photopolymerizable monomer is to give better developability

It can also be used by treating with acid anhydride.

The photopolymerizable monomer may be included in the photosensitive resin composition with respect to the total amount of 0.1 ^_0/0 to 30 parts by weight ^_0/0, for example 5 parts by weight ⁰ /. To 20 parts by weight ⁰ /.

When the photopolymerizable monomer is included in the above range, it is excellent in pattern characteristics and developability when manufacturing a color filter.

(D) photoinitiator

Examples of the photopolymerization initiator include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, and the like. Can be used.

Examples of the compounds of the acetophenone is, 2,2'-diethoxy particular when acetophenone, 2,2'-appendix when acetophenone, _{2-hydroxy-_} _ _ _2-methyl propiophenone, _{4-butyl-trichloro} _

Acetophenone, ρ-t-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2- Morpholino propane-1-one, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-S-triazine, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-lryl) -4,6-bis (trichloromethyl) -S-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -S-triazine ，

Bis (trichloromethyl) -6-styryl-S-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy Naphtho 1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2-4-trichloromethyl (piperonyl) -6-tri _, azine, 2-4-trichloromethyl ( 4'- methoxystyryl) -6-triazine, etc. are mentioned.

Examples of the oxime compound include 2- ( ₀ -benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, l- (o-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone; and the like.

The photoinitiator is a carbazole compound, diketones in addition to the compound Compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds and the like can be used.

The photomultiplier sum initiator may comprise from 0.1 weight ^_0/0 to 5 parts by weight ^_0/0, for example 1% by weight to 3 parts by weight ^_0/0 relative to the total photosensitive resin composition. When the photopolymerization initiator is included within the above range hwaeteon for color filter manufacturing ^type:

In the process, photopolymerization takes place during exposure, resulting in excellent sensitivity and improved transmittance.

(E solvent

The solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethane; Ethers such as dichloroethyl ether, _n -butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, methyl ethyl carbye, diethyl carbye, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Carbyls such as glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones, such as methyl ethyl ketone, cyclonucleanone, 4-hydroxy-4-methyl-2-pentanone, methyl-η-propyl ketone, methyl -η-butylkenone, methyl -η-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, -η-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Mesoxymethyl Acetate, Meoxyethyl Acetate, Mesoxybutyl Acetate, Ethoxymethyl Acetate, Ethoxyethyl

Acetic alkoxyalkyl esters such as acetates; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3- 3-alkoxypropionic acid alkyl esters such as ecoxypropionate; 2-hydroxy methoxy propionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionate alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxymethoxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acids such as ethyl pyruvate

Ester compounds, and also N-methylformamide, Ν, Ν-dimethylformamide, Ν-methylformanilide, Ν-methylacetamide, Ν, Ν-dimethylacetamide, Ν-methylpyridone, dimethyl Sulfoxide, benzyl ethyl ether, dinuclear ether, acetylacetone, isophorone, caproic acid _: caprylic acid, 1-octanol, 1-nonane, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.

Considering miscibility and reaction properties in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diego _. Diethylene glycols such as styrene glycol monomethyl ether;

Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.

. These solvents may be included as part cup with respect to the total amount of photosensitive resin composition, specifically, may be incorporated into 20 parts by weight ^_0/0 to 90% by weight. When the solvent is included in the above range, the coating property of the photosensitive resin composition is excellent, the thickness

Excellent flatness can be maintained in the above film. (F) other additives The photosensitive resin composition may be used to prevent spots and spots upon application, to improve leveling performance, and to prevent generation of residues by undeveloped malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling crab; Fluorine-based surfactants; Additives, such as a radical polymerization initiator, may be further included.

In addition, the photosensitive resin composition may further include an additive such as an epoxy compound in order to improve adhesiveness with a substrate.

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

The content of the additive can be easily adjusted according to the desired physical properties. Another embodiment provides a ^"color filter manufactured by using the above-described photosensitive resin composition production method of the color filter is as follows.

On the glass substrate where nothing is applied, or the protective film SiNx

On the glass substrate coated with a thickness of 500A to 1500A, the above-mentioned photosensitive resin composition for color filters is applied at a thickness of 3.1 to 3.4 jwn, respectively, using a suitable method such as spin coating or slit coating. After application, light is irradiated to form a pattern required for the color filter. After irradiating with light, the coating layer is treated with an alkali developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. By repeating this process in accordance with the required number of R, G and B colors, a color filter having a desired pattern can be obtained.

Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.

[Form for implementation of invention]

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples. (Molecular Compound Preparation)

1: synthesis of intermediate A-1)

2,4-dimethyldiphenylamine (10 mol), l-Bromo-2- (methoxymethoxy) ethane (20 mol) and sodium hydride (20 mol) were added to Ν, Ν-dimethylformamide and heated to 80 ^° C. Stir for 24 hours. Ethyl acetate was added to the solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain intermediate A-1.

Synthesis Example ² : Synthesis of Intermediate A-2

Formed by refluxing Intermediate Al (60 mmol), 3,4-dihydroxy-3-cyclobutene-1,2-dione (30 mmol) in toluene (200 mL) and butane (200 mL) Water was removed by Dean-stark distillation. After stirring for 12 hours, the green half water was distilled under reduced pressure and purified by column chromatography to obtain the intermediate A-2.

Synthesis Example 3: Synthesis of Intermediate A-3

After dissolving Intermediate A-2 (5 mmol) in 600 mL chloroform solvent, Isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL chloroform and added dropwise at room temperature for 5 hours. After 12 hours distillation under reduced pressure and separation by column chromatography gave intermediate A-3.

Synthesis Example ⁴ Synthesis of Intermediate A-4

A- intermediate A-2 (5 mmol) was dissolved in 600 mL chloroform solvent,

Add triethylamine (50 mmol). 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL chloroform and simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the product was distilled under reduced pressure and separated by column chromatography to obtain intermediate A-4.

Synthesis of -1)

B-1 ethanol Intermediate A-3 (5mmol) with 10% HC1: dichloromethane (2: 8) ⁱ into a solvent 200mL the mixture was stirred for 24 hours at 40 ^° C. After stirring, the reaction product was distilled under reduced pressure and purified by column chromatography to obtain the intermediate B-1. .

Synthesis Example 6 Synthesis of Intermediate B-2

Synthesis example except for using Intermediate A-4 instead of Intermediate A-3

Synthesis was carried out in the same manner to obtain intermediate Β-2.

7: synthesis of core-shell dye represented by formula (6))

100 mL of THF solution to which the catalytic amount of intermediate Bl (5 mmol), cyclohexyl isocyanate (8 mmol) and dibutyltin dilaurate was added was stirred under nitrogen atmosphere for 6 hours. After stirring, the reaction was distilled under reduced pressure and purified by column chromatography to obtain the formula (6).

Maldi-tof MS ： 1342.65 m / z

Synthesis Example 8: Synthesis of Core-Shell Dye represented by Chemical Formula 7

Except for using B-2 instead of the intermediate B-1 it was synthesized in the same manner as in Synthesis Example 7 to obtain a compound represented by the formula (8). _.

Maldi-tof MS ： 1344.64 m / z

(Synthesis Example 9: ^Core represented by the formula (8) Synthesis of dye shell)

2-Isocyanatoethyl acrylate instead of cyclohexyl isocyanate

Except for the synthesis in the same manner as in Synthesis Example 7 to obtain a compound represented by the formula (8).

Maldi-tof MS ： 1375.56 m / z Synthesis Example 10 Synthesis of Core-Shell Dye represented by Chemical Formula 9 Synthesis of B-2 instead of Intermediate B-1 was carried out in the same manner as in Synthesis Example 9 to obtain a compound represented by Chemical Formula 9 .

Maldi-tof MS ： 1378.53 m / z

Synthesis Example 11: Synthesis of Core-Shell Dye represented by Chemical Formula 10)

Except for using cyclohexyl isocyanate Methacryloyloxyethyl isocyanate¾- was synthesized in the same manner as in Synthesis Example 7 to obtain a compound represented by the formula (10).

Maldi-tofMS ： 1402.60 m / z

Synthesis Example Π: Synthesis of Core-Shell Dye represented by Chemical Formula 11

Synthesis was carried out in the same manner as in Synthesis Example 11 except for using B-2 instead of Intermediate B-1 to obtain a compound represented by Formula 11.

Maldi-tof MS ： 1405.59 m / z

Synthesis Example 13: Synthesis of Core-shell Dye Represented by Formula (I ² )

Synthesis was carried out in the same manner as in Synthesis Example 7 except that Phenyl isocyanate was used instead of cyclohexyl isocyanate to obtain a compound represented by Formula 12.

Maldi-tof MS: 1330.55 m / z

Synthesis Example I ⁴ : Synthesis of Core-shell Dye Represented by Formula (13)

Synthesis was carried out in the same manner as in Synthesis Example 13 except for using B-2 instead of Intermediate B-1 to obtain a compound represented by Formula 13.

Maldi-tof MS ： 1332.54 m / z

Synthesis Example I ⁵ : Synthesis of Intermediate C-1

2- (ethylanilino) ethanol (10 mol), Chloromethyl methyl ether (15 mol),

Triethylamine (15 mol) was added to dichloromethane and stirred for 24 hours. The solution was distilled under reduced pressure and separated by column chromatography to obtain Intermediate C-1ol.

Synthesis Example 16: Synthesis with Intermediate C-2

Intermediate C-2 was obtained by the same method as Synthesis Example 2, except that Intermediate C-1 was used instead of Intermediate A-1.

Synthesis Example ΙΊ: Intermediate- ³ Synthesis)

C-3 Intermediate C-3 was obtained in the same manner as in Synthesis Example 3, except that Intermediate C-2 was used instead of Intermediate A-2.

Synthesis Example 18 Synthesis of Intermediate C-4

^{^":"} Simplified increase Α-2, except instead of using the geotol intermediates C-2 to give the intermediate C-4 were synthesized in the same manner as in Synthesis Example 4.

Synthesis Example 19 Synthesis of Intermediate D-1

Synthesis was performed in the same manner as in Synthesis Example 5, except that Intermediate C-3 was used instead of Dl Intermediate A-3 to obtain Intermediate D-1. _·

Example 20: Synthesis of Intermediate D- ² )

D-2 was obtained in the same manner as in Synthesis Example 6, except that Intermediate C-4 was used instead of Intermediate A-4.

Synthesis Example 21 Synthesis of Core-shell Dye Represented by Chemical Formula 14

Synthesis was carried out in the same manner as in Synthesis Example 7, except that Intermediate D-l was used instead of Intermediate B-l to obtain a compound represented by Formula 14.

Maldi-tofMS ： 1190.58 m / z

Synthesis Example 2 ² : Synthesis of core-shell dye represented by Chemical Formula 1S Synthesis was carried out in the same manner as in Synthesis Example 21, except that Intermediate D-2 was used instead of Intermediate Dl to obtain a compound represented by Formula 15.

Maldi-tof MS ： 1193.42 m / z

Synthesis Example 23 Synthesis of Core-shell Dye Represented by Chemical Formula 16

Synthesis was carried out in the same manner as in Synthesis Example 21, except that 2-Isocyanatoethyl acrylatefi- was used instead of cyclohexyl isocyanate to obtain a compound represented by Chemical Formula 16.

Maldi-tof MS ： 1222.50 m / z

Synthesis Example 2 ⁴ : Synthesis of Core-shell Dye Represented by Chemical Formula 17

Synthesis was carried out in the same manner as in Synthesis Example 23, except that Intermediate D-2 was used instead of Intermediate D-1 to obtain a compound represented by Formula 17.

Maldi-tof MS ： 1224.49 m / z

Synthesis Example 25 Synthesis of Core-Shell Dye represented by Chemical Formula 18

It cyclohexyl isocyanate instead, and are synthesized in the same method as in Example 21 except for using Methacryloyloxyethyl soc声ate ^'to give a compound represented by the formula (18).

Maldi-tof MS ： 1251.40 m / z

Synthesis Example 26 Synthesis of Core-Shell Dye represented by Chemical Formula 19

Synthesis was carried out in the same manner as in Synthesis Example 25, except that Intermediate D-2 was used instead of Intermediate D-1 to obtain a compound represented by Formula 19.

Maldi-tof MS ： 1252.52 m / z

Synthesis Example Th Synthesis of Core-Shell Dye represented by Formula ²⁰

Phenyl isocyanate¾- was used instead of cyclohexyl isocyanate, and was synthesized in the same manner as in Synthesis Example 21 to obtain a compound represented by Formula 20.

Maldi-tofMS ： 1 178.49 m / z

Synthesis Example 28 Synthesis of Core-shell Dye Represented by Formula 21

Synthesis was carried out in the same manner as in Synthesis Example 27, except that Intermediate D-2 was used instead of Intermediate D-1 to obtain a compound represented by Formula 21.

Maldi-tof MS ： 1 180.48 m / z

Synthesis Example 29 Synthesis of Core-Shell Dye A 100mL 3-neck flask Surgical Arlene acid 398mg and 2- (3- (dibutyl-amino) phenoxy) ethyl-5 periods of time the n- butane, insert the acrylate 2.23g in 40mL and 20mL of toluene was added and 120 ^° C ¾ refluxed ¾. The Dean-Stark trap set was used to remove the reaction water and promote reaction. After completion of the reaction, the mixture was extracted, extracted with methylene chloride, and then subjected to column chromatography to obtain a compound represented by the following Chemical Formula X in 60% yield. Thereafter, 0.72 g (l mmol) of the compound represented by Chemical Formula X and 2.02 g (l mmol of triacetyl β-cyclodextrin (TCI, CAS # 23739-88-0) represented by the following Chemical Formula Y) ) Was dissolved in 50 ml of dichloromethane, and after stirring at room temperature for about 12 hours, the solvent was completely removed and dried under reduced pressure to obtain about 2.7 g of a core-shell dye in a solid state. The core-shell dye was obtained in a structure in which the compound represented by Chemical Formula X is surrounded by the compound represented by Chemical Formula Y.

[Formula X]

Synthesis Example 30 Synthesis of Compound Represented by Chemical Formula Z

[Formula Z]

Into a 100 mL flask, add 398 mg of squariaic acid and 2.23 g of 2- (3- (methyl (phenyl) amino) propylamino) ethyl acrylate, add 40 mL of n-butanol and 20 mL of toluene, and then at 120 ^° C. Heated to reflux for 5 hours. The Dean-Stark trap set was used to remove the water generated in the reaction and promote reaction. After completion of the reaction, the reaction mixture was extracted, extracted with methylene chloride and subjected to column chromatography to obtain the compound represented by Chemical Formula Z. Synthesis in 60% yield.

Maldi-tof MS ： 514.26 m / z

(Photosensitive resin composition production)

The specification of the component used for manufacture of the photosensitive resin composition is as follows. (A) dye

(A-1) Core-shell Dye Prepared in Synthesis Example 7

(A-2) Core-shell Dye Prepared in Synthesis Example 8

(A-3) Core-shell dye prepared in Synthesis Example 9 represented by Formula 8

(A-4) Core-shell dye prepared in Synthesis Example 10 (expressed by Chemical Formula 9)

(A-5) Core-shell dye prepared in Synthesis Example 11 (expressed by Formula 10) (A-6) Core-shell dye prepared in Synthesis Example 12 (expressed by Formula 11)

(A-7) Core-shell Dye Prepared in Synthesis Example 13 (Formula 12)

(A-8) Core-shell Dye Prepared in Synthesis Example (Formula 13) (A-9) Core-Shell Dye Prepared in Synthesis Example 21 (Formula 14)

(A-10) Core-shell Dye Prepared in Synthesis Example 22 (Formula 15)

(A-11) Core-Shell Dye Prepared in Synthesis Example 23 (Formula 16) (A-12) Core-Shell Dye Prepared in Synthesis Example ²⁴ (Formula II) (A-13) Core-shell dye prepared in Synthesis Example ² 5 (expressed by Chemical Formula 18)

(A-14) Core-shell Dye Prepared in Synthesis Example ² 6 (Represented by Formula 19)

(A-15) Core-shell Dye Prepared in Synthesis Example 27 (Formula 20)

(A-16) Core-shell dye prepared in Synthesis Example ² 8 (expressed by Chemical Formula 21)

(A-17) Core-shell Dye Prepared in Synthesis Example 29

(A-18) Monomolecular Dye Prepared in Synthesis Example 30 (Formula Z)

(Α ') pigment dispersion

(A'-l) C.I. Green Pigment 7

(A'-2) C.I. Green Pigment 36

B) binder resin

Methacrylic acid / benzyl methacrylate copolymer having a weight average molecular weight of 22,000 g / m (combined weight ratio 15wt% / 85wt%)

iC) photopolymerizable monomer

Nuclear acrylate to dipentaerythr

(D) photoinitiator

(D-1) 1,2-octanedione

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

(E) solvent

(E-1) cyclonucleone

(E-2) Propylene Glycol Methyl Ether Acetate Examples 1 to 16 and Comparative Examples 1 to 4

Each component was mixed with the composition of following Tables 1-3, and the photosensitive resin composition was produced. Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture is stirred at room temperature for 2 hours, and then stirred for 30 minutes by adding a dye (or pigment dispersion), and then adding a binder resin and a photopolymerizable monomer at room temperature for 2 hours. Stirred. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

TABLE 1 (Unit: weight ⁰ /。)

E-2 45 45 45 45 45 45 45 45 45

Total 100 100 100 100 100 100 100 100 100

TABLE 2

(Unit: weight ⁰ /.)

Total 100 100 100 100 100 100 100

TABLE 3

(Unit: weight%)

(evaluation) .

Evaluation 1: Durability Rating

The photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 4 was coated on a glass substrate having a thickness of imm degreasing washed, and 2 minutes on a 90 ^° C. hot plate. Drying to give a coat. After exposure using a high pressure mercury lamp having a dominant wavelength of 365 nm in the coating film, After drying in an oven at 200 ^° C for 20 minutes, the durability was confirmed by measuring the change in color coordinates using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), the results are shown in Table 4 below. Durability Evaluation Criteria

Good: color coordinate change is 0.005 or less

Poor: Change in color coordinates exceeds 0.005

TABLE 4

durability

Example 1 Good

Example 2 Good

Example 3 Good

Example 4 Good

Example 5 Good

Example 6 Good

Example 7 Good

Example 8 Good

Example 9 Good

Example 10 Good

Example 1 1 Good

Example 12 Good

Example 13 Good

Example 14 Good

Example 15 Good

Example 16 Good

Comparative Example 1 Bad

Comparative Example 2 Bad

Comparative Example 3 Good

From Table 4, in the case of Examples 1 to 16 including the core-shell dye according to one embodiment, compared with the case of Comparative Examples 1 to 4 without the core-shell dye, durability It can be seen that this increased. Evaluation 2: Luminance and Contrast Rating

The photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 4 was applied on a glass substrate having a thickness of 1 mm by degreasing washing, and then dried on a 90 ^° C. hot folate. Drying for minutes gave a coating. Subsequently, the coating film was exposed to light using a high pressure mercury lamp having a dominant wavelength of 365 nm, and then dried in a hot air circulation drying furnace ^at 200 ^° C. for 5 minutes. Pixel layer

The brightness and contrast ratio were measured using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), and the results are shown in Table 5 below.

TABLE 5

Luminance Contrast Ratio

Example 1 67.8 14800

Example 2 67.8 14600

Example 3 67.6 14500

Example 4 67.9 15700

Example 5 67.7, 15100

Example 6 67.4 14800

Example 7 67.5 14500

Example 8 67.6 14400

Example 9 67.7 15700

Example 10 67.4 14900

Example 11 67.5 15600

Example 12 67.6 14500 Example 13 67.3 15300

Example 14 67.5 15700

Example 15 67.7 15 100

Example 16 67.8 14900

Comparative Example 1 65.4 13500

Comparative Example 2 64.3 13400

Comparative Example 3 62.1 12200

Comparative Example 4 63.5 12500 From Table 5, Examples 1 to 16 including the core-shell dye according to one embodiment, Comparative Examples 1 to 4 without the core-shell dye In comparison with, it can be confirmed that high brightness and high contrast ratio can be obtained. The present invention is not limited to the above embodiments and may be manufactured in various other forms, and a person having ordinary knowledge in the art to which the present invention pertains may change the present invention without changing the technical spirit or essential features of the present invention. It will be appreciated that it may be implemented in a form. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

[Range of request]

[Claim 11

Compound represented by the following formula (1):

In Chemical Formula 1,

[Claim 2]

The method of claim 1,

R ¹ and R ² are each independently a compound represented by Formula 2 or Formula 3:

In Chemical Formulas 2 and 3,

A C3 to ^'C20 alkanes and cyclo ring or a benzene ring L ³ is a substituted or unsubstituted C1 to C10 alkylene group,

[Claim 3]

The method of claim 1,

R ³ and R ⁴ are each independently a substituted or unsubstituted C1 to C10 alkyl group or a C6 to C20 aryl group unsubstituted or substituted with a C1 to C10 alkyl group.

[Claim 4]

The method of claim 1,

Compound represented by Formula 1 is a compound represented by any one selected from the group consisting of compounds represented by the formula 1-1 to formula 1-8.

[Formula 1-1]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

1-8]

[Claim 5]

A core comprising the compound of claim 1; And

A shell surrounding the core

Core-shell dye comprising a.

[Claim 6]

According to claim 15,

The cell is a core-shell dye represented by the following formula (4) or (5).

(In Chemical Formulas 4 and 5,

V to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group)

[Claim 7]

The method of claim 5,

L ^a to L ^d are each independently substituted or unsubstituted C1 to C10 Core-shell dye which is an alkylene group.

[Claim 8]

According to claim 15,

The cell is a core-shell dye represented by the following formula 4-1 or formula -1. [Formula 4-1]

[Claim 9]

The method of claim 8, Said cell having a cage width of 6.5 A to 7.5 A.

[Claim 10]

The method of claim 5,

The core-shell dye having a length of 1nm to 3nm.

[Claim 1 1]

The method of claim 5,

The core having a maximum hop number peak at a wavelength of 530 nm to 680 nm.

[Claim 12]

The method of claim 5,

The core-shell dye is a core-shell dye represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21.

WO 2018/043829 PCT / KR2016 / 013795

[Formula 12]

.

[Formula 13]

[Formula 14]

[Formula 16]

[Formula 17]

[Claim 13]

According to claim 15,

Wherein said core-shell dye comprises said core and said shell in a molar ratio of 1: 1.

[Claim 14]

The method of claim 5,

The core-shell dye is a green dye.

[Claim 15]

A photosensitive resin composition comprising the compound of any one of claims 1 to 4 or the core-shell dye of any one of claims 5 to 14.

[Claim 16]

The method of claim 15,

The photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent.

[Claim 17]

The method of claim 16,

The photosensitive resin composition further comprises a pigment.

[Claim 18]

The method of claim 16,

The photosensitive resin composition, for a total amount of photosensitive resin composition, the compound or a core-shell dye 0.5 ^_0/0 to 10 parts by weight ^_0/0;

The binder resin 0.1 ^_0/0 to 30 parts by weight ^_0/0;

The photo-polymerization monomer 0.1 ^{^0/0} by weight to _30/0;

The photo-polymerization initiator of 0.1% increased to 5 parts by weight ⁰ /.; And

Residual solvent amount

Photosensitive resin composition comprising a.

[Claim 19]

The method of claim 16,

The photosensitive resin composition may be selected from the group consisting of malonic acid, 3-amino-1,2-propanedi, a silane coupling agent containing a vinyl group or a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. The photosensitive resin composition further containing.

[Claim 20]

The color filter manufactured using the photosensitive resin composition of Claim 15.