KR20190054408A - Novel compound, core-shell dye, photosensitive resin composition including the same, and color filter - Google Patents

Abstract

Provided are: a compound represented by chemical formula 1; a core comprising the same; a core-shell dye comprising a shell surrounding a core; a photosensitive resin composition comprising the same; and a color filter manufactured by using the photosensitive resin composition. In the chemical formula 1, each substituent is as defined in the specification. By using the compound according to an embodiment or the core-shell dye, it is possible to realize the color filter excellent in brightness and a contrast ratio.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, a core-shell dye, a photosensitive resin composition containing the same and a color filter,

The present invention relates to a novel compound, a core-shell dye, a photosensitive resin composition containing the same, and a color filter manufactured using the same.

The liquid crystal display device, which is one of the display devices, has advantages such as lightness, thinness, low cost, low power consumption driving and bonding with a good integrated circuit, and the use range thereof is expanded for notebook computers, monitors and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, and an upper substrate on which an active circuit composed of a liquid crystal layer, a thin film transistor, a capacitor capacitor layer and an ITO pixel electrode are formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield the boundary between pixels, and a plurality of colors, typically red (R), green (G), blue ) Are arranged in a predetermined order, and the pixel portions are sequentially stacked.

In the pigment dispersion method, which is one of the methods of implementing a color filter, a photopolymerizable composition containing a colorant is coated on a transparent substrate provided with a black matrix, a pattern of a pattern to be formed is exposed, And a coloring thin film is formed by repeating a series of processes of thermosetting. The colored photosensitive resin composition used in the production of a color filter according to the pigment dispersion method generally comprises an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. The pigment dispersion method is actively applied to manufacturing LCDs for mobile phones, notebooks, monitors, TVs and the like. However, recently, a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages has been required to have not only superior pattern characteristics but also further improved performance. In particular, high color rendering and high brightness and high contrast ratio characteristics 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 divided into a charge coupled device (CCD) image sensor and a complementary And a complementary metal oxide semiconductor (CMOS) image sensor. A color image pickup device used for a solid-state image pickup device or a complementary metal oxide semiconductor is a color filter (hereinafter referred to as " color filter ") having a filter segment of additive mixed primary colors of red, green, color filters) are separately installed and color-separated. In recent years, the pattern size of a color filter mounted on such a color imaging device has a size of 2 탆 or less and is 1/100 to 1/200 times that of a color filter pattern for a conventional LCD. Accordingly, the increase of the resolution and the reduction of the residue are important items that determine the performance of the device.

In a color filter made of a pigment type photosensitive resin composition, there is a limit of luminance and contrast ratio resulting from the pigment particle size. Further, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required for forming a fine pattern. In order to meet such demands, attempts have been made to introduce a dye that does not form particles instead of a pigment to produce a photosensitive resin composition suitable for a dye, thereby realizing a color filter having improved luminance and contrast ratio. However, in the case of dyes, the luminance may be lowered due to the poor durability such as light resistance and heat resistance compared with the pigment.

One embodiment is to provide a novel compound having 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 the core-shell dye.

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

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

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁴ 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,

At least one of R ¹ to R ⁴ includes an acrylate group substituted or unsubstituted at the terminal,

The acrylate group forms a direct bond with the chiral carbon.

At least one of R ¹ to R ⁴ may be represented by the following general formula (2) or (3).

(2)

In Formula 2,

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

L ¹ is represented by the following formula (2-1) or (2-2)

[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)

L ² is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁶ is a substituted or unsubstituted C1 to C10 alkyl group,

R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* Means chiral carbon,

** 1 means a moiety connected to ** in Formula 2,

** 2 means a moiety connected to the oxygen atom constituting the ether group of the formula (2).

R ¹ or R ² and R ³ or R ⁴ may each independently be represented by the following formula (3) or (4).

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

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

R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,

R ⁹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* Means chiral carbon.

R ¹ and R ³ are each independently a C 6 to C 20 aryl group substituted with a C ¹ to C 10 alkyl group, and R ² and R ⁴ may each independently be represented by the formula 3 or 4.

R ¹ and R ³ may be independently represented by the following formulas (5-1) to (5-3).

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In the above formulas 5-1 to 5-3,

R ¹⁰ to R ¹² each independently represent an unsubstituted C1 to C10 alkyl group.

The compound represented by Formula 1 may be represented by any one selected from the group consisting of compounds represented by Chemical Formulas 1-1 to 1-7.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

Another embodiment is a core comprising a compound represented by Formula 1 above; And a shell surrounding the core.

The cell may be represented by the following formula (6) or (7).

[Chemical Formula 6]

(7)

In the above formulas (6) and (7)

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

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

The cell may be represented by the following formula (6-1) or (7-1).

[Formula 6-1]

[Formula 7-1]

The cage width of the shell may be 6.5 ANGSTROM to 7.5 ANGSTROM.

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

The core may have a maximum absorption peak at a wavelength 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 formulas (8) to (21).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The core-shell dye may contain 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 comprise a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further comprise a pigment.

The photosensitive resin composition may contain 0.5 to 10% by weight of the compound or the core-shell dye, based on the total amount of the photosensitive resin composition; 0.1 to 30% by weight of the binder resin; 0.1% by weight to 30% by weight of the photopolymerizable monomer; 0.1% by weight to 5% by weight of the photopolymerization initiator; And the solvent balance.

The photosensitive resin composition may further include a silane coupling agent comprising malonic acid, 3-amino-1,2-propanediol, a vinyl group or a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, .

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

Other details of the embodiments of the present invention are included in the following detailed description.

By using the compound according to one embodiment or the core-shell dye, a color filter having excellent luminance and contrast ratio can be realized.

1 is a view showing a cage width of a shell represented by the formula (7-1).

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, " substituted " means that at least one hydrogen atom in the compound is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, A thio 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, an acid anhydride, an amide group, an azo group, an azido group, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, , 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, or a combination thereof.

Unless otherwise stated, the terms "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl Means that at least one heteroatom of N, O, S or P is present in the ring compound of the ring.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

&Quot; Combination " as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

&Quot; * " means chiral carbon unless otherwise specified herein.

Also, unless otherwise specified herein, " ** " means the same or different atom or moiety connected to the formula.

The compound according to one embodiment is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ to R ⁴ 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,

At least one of R ¹ to R ⁴ includes an acrylate group substituted or unsubstituted at the terminal,

The acrylate group forms a direct bond with the chiral carbon.

The compound represented by the above formula (1) can be used as a green dye as a compound having excellent green spectroscopic characteristics and a high molar extinction coefficient. However, since the durability of the pigment is poor, the brightness may be lowered in the baking process after the color resist is manufactured. The compound according to one embodiment has a substituent group containing a urethane linkage to improve durability, thereby realizing a color filter having a high luminance and a high contrast ratio.

In Formula 1, at least one of R ¹ to R ⁴ may be represented by Formula 2 or Formula 3 below.

(2)

In Formula 2,

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

L ¹ is represented by the following formula (2-1) or (2-2)

[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)

L ² is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁶ is a substituted or unsubstituted C1 to C10 alkyl group,

R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* Means chiral carbon,

** 1 means a moiety connected to ** in Formula 2,

** 2 means a moiety connected to the oxygen atom constituting the ether group of the formula (2).

For example, in Formula 1, at least one of R ¹ and R ² may be represented by Formula 2 or Formula 3, and at least one of R ³ and R ⁴ may be represented by Formula 2 or Formula 3.

Specifically, " R ¹ or R ² " and " R ³ or R ⁴ " may each independently be represented by the following formula (3) or (4)

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

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

R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,

R ⁹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

* Means chiral carbon.

R ¹ and R ³ are each independently a C 6 to C 20 aryl group substituted with a C ¹ to C 10 alkyl group, and R ² and R ⁴ may each independently be represented by the formula 3 or 4.

For example, R ¹ and R ³ may each independently be a C 6 to C 20 aryl group substituted with one to three C 1 to C 10 alkyl groups.

For example, R ¹ and R ³ may each independently be represented by the following formulas (5-1) to (5-3).

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In the above formulas 5-1 to 5-3,

R ¹⁰ to R ¹² each independently represent an unsubstituted C1 to C10 alkyl group.

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

The compound represented by Formula 1 may have excellent heat resistance. That is, the thermal decomposition temperature when measured by a thermogravimetric analyzer (TGA) may be 200 ° C or higher, for example, 200 ° C to 300 ° C.

The compound represented by the formula (1) has three resonance structures as shown in the following diagram, but for the sake of convenience, the compound represented by the formula (1) is merely represented by one resonance structure. That is, the compound represented by Formula 1 may be represented by any one of the three resonance structures.

[scheme]

The compound represented by Formula 1 may be represented by any one selected from the group consisting of compounds represented by Chemical Formulas 1-1 to 1-7.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

The core-shell dye according to another embodiment may have a structure consisting of a core and a shell surrounding the core. The core comprises a compound represented by the above formula (1). Specifically, the shell may be a macrocyclic compound, and the shell may form a coating layer while surrounding the compound represented by the formula (1).

In one embodiment, the shell corresponding to the macrocyclic compound has a structure in which the compound represented by the formula (1) is present in the macrocycle due to the structure surrounding the compound represented by the formula (1) It is possible to improve the durability of the core-shell dye, thereby realizing a color filter of high luminance and high contrast ratio.

The length of the compound contained in the core or represented by the formula (1) constituting the core may be 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the compound represented by Formula 1 has a length within the above range, it is possible to easily form a core-shell dye having a structure of a core and a shell surrounding the core. In other words, as the compound represented by the formula (1) has a length within the range, the shell as the macrocyclic compound can be obtained in a structure surrounding the compound represented by the formula (1). It is difficult to expect improvement in durability because it is difficult to form a structure surrounding the compound which is a core of the shell when another compound which does not correspond to the length of the above range is used.

The compound contained in the core or the compound represented by the formula (1) constituting the core may have a maximum absorption peak at a wavelength of 530 nm to 680 nm. By using the core-shell dye using the compound represented by the above formula (1) having the spectroscopic characteristics as a core, for example, as a green dye, a photosensitive resin composition for a color filter having a high brightness and a high contrast ratio can be obtained.

The shell surrounding the core comprising the compound represented by Formula 1 may be represented by Formula 6 or Formula 7 below.

[Chemical Formula 6]

(7)

In the above formulas (6) and (7)

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

In the formula (6) or (7), L ^a to L ^d each independently represent a substituted or unsubstituted C1 to C10 alkylene group. In this case, the solubility is excellent, and the shell tends to form a structure surrounding the core containing the compound represented by the above formula (1).

For example, the core-shell dye according to one embodiment is a non-covalent bond between the oxygen atom of the compound represented by the formula (1) and the hydrogen atom bonding to the nitrogen atom of the shell represented by the formula (6) or (7) . ≪ / RTI >

The shell may be represented by, for example, the following formula (6-1) or (7-1).

[Formula 6-1]

[Formula 7-1]

The cage width of the shell may be 6.5 ANGSTROM to 7.5 ANGSTROM, and the volume of the shell may be 10 ANGSTROM to 16 ANGSTROM. Herein, the cage width means a distance between two different phenylene groups in which a methylene group is connected on both sides of the shell, for example, in the shell represented by the above formula (6-1) or (7-1) (See Fig. 1). When the shell has a cage width within the above range, it is possible to obtain a core-shell dye having a structure which surrounds the core including the compound represented by the formula (1), and thus the core-shell dye is added to the photosensitive resin composition A color filter having excellent durability and high brightness can be realized.

The core-shell dye may include a core containing the compound represented by Formula 1 and the shell in a molar ratio of 1: 1. When the core and the shell are present in the above-mentioned molar ratio, a coating layer (shell) surrounding the core containing the compound represented by the formula (1) can 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 formulas (8) to (21), but is not limited thereto.

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The core-shell dye may be used alone as a green dye, or may be mixed with a coloring dye.

Examples of the coloring dye include triarylmethane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azapphyrin dyes, indigo dyes, xanthene dyes, pyridonazo dyes, etc. .

The core-shell dye may also be used in admixture with a pigment.

As the pigment, a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment and the like can be used.

Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89 and the like. Examples of the green pigment include C.I. Green pigment 7, C.I. Green pigment 36, C.I. Green pigment 58, C.I. Green pigment 59 and the like. Examples of the blue pigments include C.I. Blue pigment 15: 6, C.I. Blue pigment 15, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I. Blue pigment 16, and the like. Examples of the yellow pigments include C.I. Yellow pigments 139 and the like, C.I. Quinophthalone-based pigments such as yellow pigment 138 and the like, C.I. And yellow complex pigments such as yellow pigment 150 and the like. Examples of the black pigment include aniline black, perylene black, titanium black, and carbon black. These pigments can be used singly or in combination of two or more thereof, but are not limited to these examples.

The pigment may be included in the photosensitive resin composition for a color filter in the form of a dispersion. Such a pigment dispersion may be composed of the pigment, a solvent, a dispersant, a dispersion resin, or the like.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used. Among them, propylene glycol methyl ether acetate is preferably used .

The dispersant helps to uniformly disperse the pigment in the dispersion, and any nonionic, anionic or cationic dispersant may be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts Water, alkylamine, and the like. These may be used alone or in combination of two or more.

The dispersion resin may use an acrylic resin containing a carboxyl group, which not only improves the stability of the pigment dispersion but also improves the patterning of pixels.

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

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

The photosensitive resin composition contains (A) a colorant (the compound represented by the above formula (1) or the core-shell dye), (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and can do.

Each component will be described in detail below.

(A) Colorant

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

The colorant may further include a pigment in addition to the compound represented by Formula 1 and / or the core-shell dye, and the pigment has been described above.

The compound represented by Formula 1 and / or the core-shell dye may be contained in an amount of 0.5 to 10% by weight, for example, 0.5 to 5% by weight based on the total amount of the photosensitive resin composition for a color filter. When the core-shell dye is used within the above range, high brightness and contrast ratio can be expressed in a desired color coordinate.

(B) binder resin

The binder resin may contain a first ethylenic unsaturated monomer 　 And a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing at least one acrylic repeating unit.

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

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

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the binder resin include a methacrylic acid / benzyl methacrylate copolymer, a methacrylic acid / benzyl methacrylate / styrene copolymer, a methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer , Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used alone or in combination of two or more.

The weight average molecular weight of the binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the binder resin is within the above range, it has good adhesion with the substrate, good physical and chemical properties, and good viscosity.

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

The binder resin may be contained in an amount of 0.1% by weight to 30% by weight, for example, 5% by weight to 20% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, the color filter is excellent in developability in the production of a color filter and the cross-linkability is improved, so that excellent surface smoothness can be obtained.

(C) Photopolymerization  Monomer

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

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as 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 tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 0.1% by weight to 30% by weight, for example, 5% by weight to 20% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, pattern characteristics and developability are excellent in the production of a color filter.

(D) Light curing Initiator

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

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

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.

Examples of the oxime compounds include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a nonimidazole compound, or a fluorene compound in addition to the above compounds.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently during exposure in the pattern formation process for producing a color filter, and the sensitivity is excellent and the transmittance is improved.

(E) Solvent

The solvent is not particularly limited, but specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl 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 and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic 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-methylpropionic acid 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-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included as a remainder with respect to the total amount of the photosensitive resin composition, specifically 20 wt% to 90 wt%. When the solvent is contained within the above range, the photosensitive resin composition is excellent in coating property and excellent flatness can be maintained in a film having a thickness of 3 m or more.

(F) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; A radical polymerization initiator, and the like.

The above-mentioned photosensitive resin composition may further contain an additive such as an epoxy compound in order to improve the adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The content of the additive can be easily adjusted according to desired properties.

Another embodiment provides a color filter manufactured using the above-described photosensitive resin composition. A method of manufacturing the color filter is as follows.

The above-mentioned photosensitive resin composition for a color filter is applied onto a glass substrate to which nothing is applied or a glass substrate on which a protective film such as SiN _x is applied to a thickness of 500 to 1500 ANGSTROM by a suitable method such as spin coating or slit coating And a thickness of 3.1 mu m to 3.4 mu m, respectively. After the application, light is irradiated to form a pattern necessary for the color filter. After the light is irradiated and the coating layer is treated with an alkali developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained.

In addition, in the above process, the image pattern obtained by development may be further heated or cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

( Single molecule  Compound Preparation)

( Synthetic example  1: Synthesis of intermediate A-1)

[Reaction Scheme 1]

Aniline (10 mol), 1-Bromo-2,4-dimethyl-benzene (10 mol), Pd ₂ (dba) ₃ (0.1 mol) and Xphos (0.1 mol) were placed in toluene, Lt; / RTI > Ethyl acetate was added to this solution and the mixture was 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-1.

( Synthetic example  2: Synthesis of intermediate A-2)

Synthesis was conducted in the same manner as in Synthesis Example 1 except that 4-Bromotoluene was used instead of 1-Bromo-2,4-dimethyl-benzene to obtain Intermediate A-2.

( Synthetic example  3: Synthesis of intermediate A-3)

Synthesis was conducted in the same manner as in Synthesis Example 1 except that Mesityl Bromide was used instead of 1-Bromo-2,4-dimethyl-benzene to obtain Intermediate A-3

( Synthetic example  4: Synthesis of Intermediate B-1)

[Reaction Scheme 2]

Intermediate A-1 (10 mol), 1,2-butylene oxide (10 mol) and sodium hydride (12 mol) were added to N, N-dimethylformamide and the mixture was heated to 90 ° C and stirred for 24 hours. Ethyl acetate was added to this solution and the mixture was washed twice with water to extract an organic layer. The extracted organic layer was subjected to vacuum distillation and separated by column chromatography to obtain Intermediate B-1.

( Synthetic example  5: Synthesis of Intermediate B-2)

Intermediate B-2 was obtained in the same manner as in Synthesis Example 4 except that Intermediate A-2 was used instead of Intermediate A-1.

( Synthetic example  6: Synthesis of Intermediate B-3)

Intermediate B-3 was obtained in the same manner as in Synthesis Example 4 except that Intermediate A-3 was used instead of Intermediate A-1.

( Synthetic example  7: Synthesis of Intermediate B-4)

Synthesis was conducted in the same manner as in Synthesis Example 4 except that 2,3-butylene oxide was used instead of 1,2-butylene Oxide to obtain Intermediate B-4.

( Synthetic example  8: Synthesis of Intermediate B-5)

Synthesis was conducted in the same manner as in Synthesis Example 4 except that 1,2-Epoxypentane was used instead of 1,2-Butylene Oxide to obtain Intermediate B-5.

( Synthetic example  9: Synthesis of Intermediate B-6)

Synthesis was carried out in the same manner as in Synthesis Example 4, except that 1,2-epoxyhexane was used instead of 1,2-butylene Oxide to obtain Intermediate B-6.

( Synthetic example  10: Synthesis of Intermediate B-7)

Synthesis was conducted in the same manner as in Synthesis Example 4 except that 1,2-Epoxycyclohexane was used instead of 1,2-Butylene Oxide to obtain Intermediate B-7.

( Synthetic example  11: Synthesis of Intermediate C-1)

[Reaction Scheme 3]

Intermediate B-1 (10 mmol), Methacryloyl Chloride (10 mmol), and triethylamine (15 mmol) were added to N, N-dimethylformamide and stirred at room temperature for 24 hours. Ethyl acetate was added to this solution and the mixture was washed twice with water to extract an organic layer. The extracted organic layer was subjected to vacuum distillation and separated by column chromatography to obtain Intermediate C-1.

( Synthetic example  12: Synthesis of Intermediate C-2)

Intermediate C-2 was obtained in the same manner as in Synthesis Example 11 except for using Intermediate B-2 instead of Intermediate B-1.

( Synthetic example  13: Synthesis of Intermediate C-3)

Intermediate C-3 was obtained in the same manner as in Synthesis Example 11 except that Intermediate B-3 was used instead of Intermediate B-1.

( Synthetic example  14: Synthesis of intermediate C-4)

Intermediate C-4 was obtained in the same manner as in Synthesis Example 11 except that Intermediate B-4 was used instead of Intermediate B-1.

( Synthetic example  15: Synthesis of Intermediate C-5)

Intermediate C-5 was obtained in the same manner as in Synthesis Example 11 except for using Intermediate B-5 instead of Intermediate B-1.

( Synthetic example  16: Synthesis of Intermediate C-6)

Synthesis was conducted in the same manner as in Synthesis Example 11 except that Intermediate B-6 was used instead of Intermediate B-1 to obtain Intermediate C-6.

( Synthetic example  16: Synthesis of Intermediate C-7)

Intermediate C-7 was obtained in the same manner as in Synthesis Example 11 except for using Intermediate B-7 instead of Intermediate B-1.

( Synthetic example  17: Synthesis of Compound Represented by Formula 1-1)

[Reaction Scheme 4]

Intermediate C-1 (60 mmol) and 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30 mmol) were added to toluene (200 mL) and butanol The water is removed with a Dean-stark distillation apparatus. After stirring for 12 hours, the green reaction product was distilled under reduced pressure and purified by column chromatography to obtain the compound represented by Formula 1-1 (Maldi-tof MS: 752.38 m / z).

( Synthetic example  18: Synthesis of Compound Represented by Formula 1-2)

Synthesis was conducted in the same manner as in Synthesis Example 17 except that Intermediate C-2 was used in place of Intermediate C-1 to obtain a compound represented by the following Formula 1-2.

[Formula 1-2]

Maldi-tof MS: 724.35 < RTI ID = 0.0 > m / z

( Synthetic example  19: Synthesis of Compound Represented by Formula 1-3)

Synthesis was conducted in the same manner as in Synthesis Example 17 except that Intermediate C-3 was used instead of Intermediate C-1 to obtain a compound represented by the following Formula 1-3.

[Formula 1-3]

Maldi-tof MS: 780.41 m / z

( Synthetic example  20: Synthesis of Compound Represented by Formula 1-4)

Synthesis was conducted in the same manner as in Synthesis Example 17 except that Intermediate C-4 was used in place of Intermediate C-1 to obtain a compound represented by the following formula 1-4.

[Formula 1-4]

Maldi-tof MS: 752.38 m / z

( Synthetic example  21: Synthesis of Compound Represented by Formula 1-5)

Synthesis was conducted in the same manner as in Synthesis Example 17 except that Intermediate C-5 was used instead of Intermediate C-1 to obtain a compound represented by the following formula (1-5).

[Formula 1-5]

Maldi-tof MS: 780.41 m / z

( Synthetic example  22: Synthesis of the compound represented by the general formula 1-6)

Synthesis was conducted in the same manner as in Synthesis Example 17 except that Intermediate C-6 was used instead of Intermediate C-1 to obtain a compound represented by the following formula 1-6.

[Chemical Formula 1-6]

Mald-tof MS: 808.45m / z

( Synthetic example  23: Synthesis of Compound Represented by Formula 1-7)

Synthesis was conducted in the same manner as in Synthesis Example 17 except for using Intermediate C-7 instead of Intermediate C-1 to obtain a compound represented by the following formula 1-7.

[Chemical Formula 1-7]

Mald-tof MS: 804.41m / z

( Synthetic example  24: Synthesis of Intermediate D-1)

[Reaction Scheme 5]

2-Bromoethanol (10 mmol), 3,4-Dihydro-2H-pyran (10 mmol) and p-toluenesulfonic acid monohydrate (0.05 mmol) were added to dichloromethane and stirred for 1 hour. Ethyl acetate was added to this solution and the mixture was washed twice with water to extract an organic layer. Intermediate A-1 is added to N, N-dimethylformamide, and sodium hydride (12 mol) is added dropwise thereto, followed by stirring for 2 hours. The organic matter extracted from above is added dropwise and stirred for 12 hours. Ethyl acetate is added to this solution, and the solution is washed twice with water. The organic layer is extracted and the solvent is removed. The solution is added dropwise to methanol with p-toluenesulfonic acid monohydrate (0.05 mmol). After stirring for 2 hours, ethyl acetate was added and the mixture was washed twice with water. The organic layer was extracted, the solvent was removed, and the product was separated by column chromatography to obtain Intermediate D-1.

( Synthetic example  25: Synthesis of Intermediate D-2)

Synthesis was conducted in the same manner as in Synthesis Example 24 except that 5-bromo-1-pentanol was used in place of 2-bromoethanol to obtain Intermediate D-2.

( Synthetic example  26: Synthesis of Intermediate E-1)

Intermediate E-1 was obtained in the same manner as in Synthesis Example 11 except for using Intermediate D-1 instead of Intermediate B-1.

( Synthetic example  27: Synthesis of Intermediate E-2)

Intermediate E-2 was obtained in the same manner as in Synthesis Example 11 except for using Intermediate D-2 instead of Intermediate B-1.

( Comparative Synthetic Example  1: Synthesis of the compound represented by the formula (F-1)

Synthesis was conducted in the same manner as in PREPARATION 17, except that Intermediate E-1 was used instead of Intermediate C-1 to obtain a compound represented by the following formula F-1.

[Formula F-1]

Maldi-tof MS: 696.32 < RTI ID = 0.0 > m / z

( Comparative Synthetic Example  2: Synthesis of the compound represented by the formula (F-2)

Synthesis was conducted in the same manner as in PREPARATION 17, except that Intermediate E-2 was used instead of Intermediate C-1 to obtain a compound represented by the following formula F-2.

[Formula F-2]

Maldi-tof MS: 780.41 m / z

(Synthesis of core-shell dye)

( Synthetic example  28: Synthesis of core-shell dye represented by formula (8)

[Reaction Scheme 6]

The compound (5 mmol) represented by formula (1-1) is dissolved in 600 mL of chloroform, and isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL of chloroform and simultaneously dripped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure, and the residue was purified by column chromatography to obtain the compound represented by Formula 8 (Maldi-tof MS: 1284.59 m / z).

( Synthetic example  29: Synthesis of core-shell dye represented by formula (9)

[Reaction Scheme 7]

Compound (5 mmol) represented by formula (1-1) was dissolved in chloroform (600 mL), and triethylamine (50 mmol) was added thereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform and simultaneously dropped at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure, and the residue was purified by column chromatography to obtain the compound represented by Formula 9 (Maldi-tof MS: 1286.58 m / z).

( Synthetic example  30: To 10  Synthesis of the indicated core-shell dye)

Was synthesized in the same manner as in Synthesis Example 28, except that the compound represented by Formula (1-2) was used instead of the compound represented by Formula (1-1) to give a compound represented by Formula (10).

[Chemical formula 10]

Mald-tof MS: 1256.56 m / z

( Synthetic example  31: Synthesis of core-shell dye represented by formula (11)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula (1-2) was used instead of the compound represented by Formula (1-1) to obtain a compound represented by Formula (11).

(11)

Mald-tof MS: 1258.55 m / z

( Synthetic example  32: Synthesis of core-shell dye represented by formula (12)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula 1-3 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula 12 below.

[Chemical Formula 12]

Mald-tof MS: 1312.62m / z

( Synthetic example  33: To 13  Synthesis of the indicated core-shell dye)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula (1-3) was used instead of the compound represented by Formula (1-1) to obtain a compound represented by Formula (13).

[Chemical Formula 13]

Mald-tof MS: 1314.62m / z

( Synthetic example  34: Synthesis of core-shell dye represented by formula (14)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula (1-4) was used instead of the compound represented by Formula (1-1) to obtain a compound represented by Formula (14).

[Chemical Formula 14]

Mald-tof MS: 1284.59 m / z

( Synthetic example  35: Synthesis of core-shell dye represented by formula (15)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula 1-4 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula 15 below.

[Chemical Formula 15]

Maldi-tof MS: 1286.58 m / z

( Synthetic example  36: To 16  Synthesis of the indicated core-shell dye)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula (1-5) was used instead of the compound represented by Formula (1-1) to obtain a compound represented by Formula (16).

[Chemical Formula 16]

Mald-tof MS: 1232.62 m / z

( Synthetic example  37: Synthesis of core-shell dye represented by formula (17)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula (1-5) was used instead of the compound represented by Formula (1-1) to obtain a compound represented by Formula (17).

[Chemical Formula 17]

Mald-tof MS: 1314.62m / z

( Synthetic example  38: Synthesis of core-shell dye represented by formula (18)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula 1-6 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula 18 below.

[Chemical Formula 18]

Maldi-tof MS: 1340.66 m / z

( Synthetic example  39: Synthesis of core-shell dye represented by formula (19)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula 1-6 was used instead of the compound represented by Formula 1-1 to give a compound represented by Formula 19 below.

[Chemical Formula 19]

Maldi-tof MS: 1342.65 m / z

( Synthetic example  40: Synthesis of core-shell dye represented by formula (20)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula 1-7 was used instead of the compound represented by Formula 1-1 to give a compound represented by Formula 20 below.

[Chemical Formula 20]

Mald-tof MS: 1336.62 m / z

( Synthetic example  41: To 21  Synthesis of the indicated core-shell dye)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula 1-7 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula 21.

[Chemical Formula 21]

Mald-tof MS: 1338.62 m / z

( Comparative Synthetic Example  3: To 1  Synthesis of the indicated core-shell dye)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula F-1 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula G-1.

[Formula G-1]

Mald-tof MS: 1228.53 m / z

( Comparative Synthetic Example  4: Synthesis of core-shell dye represented by formula G-2)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula F-1 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula G-2.

[Formula G-2]

Mald-tof MS: 1230.52 m / z

( Comparative Synthetic Example  5: Synthesis of core-shell dye represented by the formula G-3)

Was synthesized in the same manner as in Synthesis Example 28 except that the compound represented by Formula F-2 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula G-3.

[Formula G-3]

Mald-tof MS: 1312.62 m / z

( Comparative Synthetic Example  6: Synthesis of core-shell dye represented by the formula G-4)

Was synthesized in the same manner as in Synthesis Example 29 except that the compound represented by Formula F-2 was used instead of the compound represented by Formula 1-1 to obtain a compound represented by Formula G-4.

[Formula G-4]

Mald-tof MS: 1314.62 m / z

( Comparative Synthesis Example 7: Synthesis of core-shell dye)

398 mg of squalic acid and 2.23 g of 2- (3- (dibutylamino) phenoxy) ethyl acrylate were placed in a 100 mL three-necked flask, and 40 mL of n-butanol and 20 mL of toluene were added. Respectively. Dean-Stark trap set was used to remove the water generated during the reaction and promote the reaction. After completion of the reaction, the reaction mixture was cooled, extracted with methylene chloride, and then subjected to column chromatography to obtain a compound represented by the following formula (X) in a yield of 60%. Thereafter, 0.72 g (1 mmol) of the compound represented by the above formula (X) and 2.02 g (1 mmol) of triacetyl beta-cyclodextrin (TCI, CAS # 23739-88-0) ) Was dissolved in 50 ml of dichloromethane. After stirring for about 12 hours at room temperature, 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 the formula (X) was surrounded by the compound represented by the formula (X).

(X)

[Formula Y]

(Preparation of photosensitive resin composition)

The specifications of the components used in the production of the photosensitive resin composition are as follows.

(A) Dye

(A-1) The core-shell dye (represented by the formula (8)) prepared in Synthesis Example 8,

(A-2) The core-shell dye (represented by the formula (9)) prepared in Synthesis Example 9,

(A-3) The core-shell dye (represented by Formula 10) prepared in Synthesis Example 10,

(A-4) The core-shell dye prepared in Synthesis Example 11 (represented by Formula 11)

(A-5) The core-shell dye (represented by the formula (12)) prepared in Synthesis Example 12,

(A-6) The core-shell dye (represented by the formula (13)) prepared in Synthesis Example 13,

(A-7) The core-shell dye prepared in Synthesis Example 14 (represented by Formula 14)

(A-8) The core-shell dye (represented by formula (15)) prepared in Synthesis Example 15,

(A-9) The core-shell dye prepared in Synthesis Example 16 (represented by Formula 16)

(A-10) The core-shell dye prepared in Synthesis Example 17 (represented by Formula 17)

(A-11) The core-shell dye prepared in Synthesis Example 18 (represented by Formula 18)

(A-12) The core-shell dye prepared in Synthesis Example 19 (represented by Formula 19)

(A-13) The core-shell dye prepared in Synthesis Example 20 (represented by Formula 20)

(A-14) The core-shell dye prepared in Synthesis Example 21 (represented by Formula 21)

(A-15) The core-shell dye (represented by the formula G-1) prepared in Comparative Synthesis Example 3,

(A-16) The core-shell dye (represented by the formula G-2) prepared in Comparative Synthesis Example 4,

(A-17) The core-shell dye (represented by the formula G-3) prepared in Comparative Synthesis Example 5,

(A-18) The core-shell dye (represented by the formula G-4) prepared in Comparative Synthesis Example 6,

(A-19) The core-shell dye prepared in Comparative Synthesis Example 7

(A ') Pigment dispersion

(A'-1) 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 / mol (mixing weight ratio 15wt% / 85wt%),

(C) Photopolymerization  Monomer

Dipentaerythritol hexaacrylate

(D) Light curing Initiator

(D-1) 1,2-octanedione

(D-2) To a solution of 2-dimethylamino-2- (4-methyl-benzyl)

(E) Solvent

(E-1) cyclohexanone

(E-2) Propylene glycol methyl ether acetate

Example  1 to Example  14 and Comparative Example  1 to Comparative Example  7

Each component was mixed with the compositions shown in Tables 1 to 3 below to prepare a photosensitive resin composition. Specifically, a photopolymerization initiator was dissolved in a solvent and stirred for 2 hours at room temperature. Then, a dye (or a pigment dispersion) was added thereto and stirred for 30 minutes. Then, a binder resin and a photopolymerizable monomer were added, Lt; / RTI > The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

(Unit: wt%) Example One 2 3 4 5 6 7 8 (A) Dye A-1 2 - - - - - - - A-2 - 2 - - - - - - A-3 - - 2 - - - - - A-4 - - - 2 - - - - A-5 - - - - 2 - - - A-6 - - - - - 2 - - A-7 - - - - - - 2 - A-8 - - - - - - - 2 (A ') Pigment dispersion A'-1 - - - - - - - - A'-2 - - - - - - - - (B) binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) a photopolymerizable monomer 8 8 8 8 8 8 8 8 (D) a photopolymerization initiator D-1 One One One One One One One One D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent E-1 40 40 40 40 40 40 40 40 E-2 45 45 45 45 45 45 45 45 Total 100 100 100 100 100 100 100 100

(Unit: wt%) Example 9 10 11 12 13 14 (A) Dye A-9 2 - - - - - A-10 - 2 - - - - A-11 - - 2 - - - A-12 - - - 2 - - A-13 - - - - 2 - A-14 - - - - - 2 (A ') Pigment dispersion A'-1 - - - - - - A'-2 - - - - - - (B) binder resin 3.5 3.5 3.5 3.5 3.5 3.5 (C) a photopolymerizable monomer 8 8 8 8 8 8 (D) a photopolymerization initiator D-1 One One One One One One D-2 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent E-1 40 40 40 40 40 40 E-2 45 45 45 45 45 45 Total 100 100 100 100 100 100

(Unit: wt%) Comparative Example One 2 3 4 5 6 7 (A) Dye A-15 2 - - - - - - A-16 - 2 - - - - - A-17 - - 2 - - - - A-18 - - - 2 - - - A-19 - - - - 2 - - (A ') Pigment dispersion A'-1 - - - - - 2 - A'-2 - - - - - - 2 (B) binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) a photopolymerizable monomer 8 8 8 8 8 8 8 (D) a photopolymerization initiator D-1 One One One One One One One D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Solvent E-1 40 40 40 40 40 40 40 E-2 45 45 45 45 45 45 45 Total 100 100 100 100 100 100 100

(evaluation)

Evaluation 1: Durability evaluation

The photosensitive resin composition prepared in Examples 1 to 14 and Comparative Examples 1 to 7 was coated on a 1 mm thick glass substrate having a thickness of 1 mu m to 3 mu m, Min to obtain a coating film. Subsequently, the coated film was exposed to light using a high-pressure mercury lamp having a main wavelength of 365 nm, dried in an oven at 200 ° C. for 20 minutes, and then the color coordinate change value was measured using a spectrophotometer (MCPD3000, Otsuka electronic) Durability was confirmed, and the results are shown in Table 4 below.

Durability evaluation standard

Good: When the color coordinate change value is 0.005 or less

Poor: color coordinate change value exceeds 0.005

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 11 Good Example 12 Good Example 13 Good Example 14 Good Comparative Example 1 Bad Comparative Example 2 Bad Comparative Example 3 Good Comparative Example 4 Good Comparative Example 5 Good Comparative Example 6 Good Comparative Example 7 Bad

From Table 4, it can be confirmed that the photosensitive resin compositions according to Examples 1 to 14 including the core-shell dye according to one embodiment have excellent durability.

Evaluation 2: Evaluation of luminance and contrast

The photosensitive resin composition prepared in Examples 1 to 14 and Comparative Examples 1 to 7 was coated on a glass substrate having a thickness of 1 mm and washed to a thickness of 1 탆 to 3 탆, Min to obtain a coating film. Subsequently, the coated film was exposed using a high-pressure mercury lamp having a main wavelength of 365 nm, and then dried in a hot-air circulating drying furnace at 200 ° C for 5 minutes. The pixel layer was measured for brightness and contrast ratio using a spectrophotometer (MCPD3000, Otsuka electronic Co.), and the results are shown in Table 5 below.

Luminance Contrast ratio Example 1 67.2 14800 Example 2 67.1 14900 Example 3 67.3 14900 Example 4 67.2 14800 Example 5 67.4 15100 Example 6 67. 5 15200 Example 7 67.6 15300 Example 8 67.7 15000 Example 9 67.3 14900 Example 10 67.1 14700 Example 11 67.2 14800 Example 12 67.3 15100 Example 13 67.1 14900 Example 14 67.2 14700 Comparative Example 1 64.7 13200 Comparative Example 2 64.5 13100 Comparative Example 3 65.3 14100 Comparative Example 4 65.1 13800 Comparative Example 5 65.3 13900 Comparative Example 6 65.5 14000 Comparative Example 7 64.9 13200

From Table 5, it can be seen that, in the case of Examples 1 to 14 including the core-shell dye according to one embodiment, as compared with the case of Comparative Examples 1 to 7 which do not include the core-shell dye, And a high contrast ratio can be obtained.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (22)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ¹ to R ⁴ 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,
At least one of R ¹ to R ⁴ includes an acrylate group substituted or unsubstituted at the terminal,
The acrylate group forms a direct bond with the chiral carbon.
The method according to claim 1,
Wherein at least one of R ¹ to R ⁴ is represented by the following formula 2 or 3:
(2)

In Formula 2,
R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is represented by the following formula (2-1) or (2-2)
[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)
L ² is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,
R ⁶ is a substituted or unsubstituted C1 to C10 alkyl group,
R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
* Means chiral carbon,
** 1 means a moiety connected to ** in Formula 2,
** 2 means a moiety connected to the oxygen atom constituting the ether group of the formula (2).
The method according to claim 1,
Wherein R ¹ or R ² and R ³ or R ⁴ are each independently a compound represented by the following formula 3 or 4:
(3)

[Chemical Formula 4]

In the above formulas (3) and (4)
L ³ is a substituted or unsubstituted C1 to C10 alkylene group,
R ⁸ is a substituted or unsubstituted C1 to C10 alkyl group,
R ⁹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
* Means chiral carbon.
The method of claim 3,
Wherein R ¹ and R ³ are each independently a C 6 to C 20 aryl group substituted with a C ¹ to C 10 alkyl group,
And R < ² > and R < ⁴ > are each independently a group represented by the formula (3) or (4).
5. The method of claim 4,
Wherein R ¹ and R ³ are each independently a group represented by the following formulas (5-1) to (5-3):
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In the above formulas 5-1 to 5-3,
R ¹⁰ to R ¹² each independently represent an unsubstituted C1 to C10 alkyl group.
The method according to claim 1,
The compound represented by the formula (1) is represented by any one selected from the group consisting of compounds represented by the following formulas (1-1) to (1-7).
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

A core comprising the compound of claim 1; And
The shell surrounding the core
≪ / RTI >
8. The method of claim 7,
Wherein the cell is represented by the following formula (6) or (7).
[Chemical Formula 6]

(7)

(In the formulas (6) and (7)
L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group)
9. The method of claim 8,
Wherein L ^a to L ^d are each independently a substituted or unsubstituted C 1 to C 10 alkylene group.
9. The method of claim 8,
Wherein the cell is represented by the following formula (6-1) or (7-1).
[Formula 6-1]

[Formula 7-1]

11. The method of claim 10,
Wherein the cell has a cage width of 6.5 ANGSTROM to 7.5 ANGSTROM.
8. The method of claim 7,
Wherein the core has a length of 1 nm to 3 nm.
8. The method of claim 7,
Wherein the core has a maximum absorption peak at a wavelength of from 530 nm to 680 nm.
8. The method of claim 7,
Wherein the core-shell dye is represented by any one selected from the group consisting of compounds represented by the following formulas (8) to (21).
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

8. The method of claim 7,
Wherein the core-shell dye comprises the core and the shell in a molar ratio of 1: 1.
8. The method of claim 7,
Wherein the core-shell dye is a green dye.
A photosensitive resin composition comprising the compound of any one of claims 1 to 6 or the core-shell dye of any one of claims 7 to 16.
18. The method of claim 17,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.
19. The method of claim 18,
Wherein the photosensitive resin composition further comprises a pigment.
19. The method of claim 18,
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
0.5 to 10% by weight of said compound or core-shell dye;
0.1 to 30% by weight of the binder resin;
0.1% by weight to 30% by weight of the photopolymerizable monomer;
0.1% by weight to 5% by weight of the photopolymerization initiator; And
The solvent balance
.
19. The method of claim 18,
The photosensitive resin composition may further include a silane coupling agent comprising malonic acid, 3-amino-1,2-propanediol, a vinyl group or a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, .
A color filter produced by using the photosensitive resin composition of claim 17.

Images