KR20160129385A - Colored Dye for color filter and Preparation method thereof - Google Patents

Abstract

The present invention relates to a colored dye for a color filter and a photosensitive resin composition containing the same. More specifically, by introducing a specific ionic substituent group such as cyanoetecetic acid group capable of improving solubility in phthalocyanine and substituting a strong electron withdrawing group capable of improving the solubility in a solvent, To provide a coloring dye for a color filter having high brightness and excellent in heat resistance, light resistance and chemical resistance, and a photosensitive resin composition containing the same.

Description

Colored dyes for color filters and photosensitive resin compositions containing them [0002]

The present invention relates to a colored dye for a color filter, which is a tetraazapopyrin system having a specific structure having at least one electron withdrawing group in a molecule, and a photosensitive resin composition containing the same.

In order to realize color, a color filter has a color filter having three colors of red, green and blue (liquid crystal) on the liquid crystal, thereby realizing a natural color by adjusting the ratio of light passing through the color filter.

The main colorant for such a color filter is prepared by a method of forming a desired coloring pattern using a colored photosensitive resin composition containing a pigment. However, recently, there is a growing demand for high-performance products such as large-sized LCD TVs, high-color reproduction, and high brightness. Thus, research on various colored photosensitive compositions having blue, red or green colors excellent in color brightness and color purity ought.

Particularly, these colorant pigments have excellent fastness to heat and light, but they are not dissolved in solvents, and thus they can be applied to high-performance displays such as large LCD TVs requiring color brightness and high brightness characteristics.

Therefore, many studies have been made to increase the solubility of dyes by introducing an organic functional group into a pigment not dissolved in a solvent.

For example, in Korean Patent Laid-Open Publication No. 2011-0123616, SO ₃ ^- or CO ₃ ^- is introduced into a terminal group of phthalocyanine used as a conventional blue pigment to form an ionic bond with a cationic substance such as Na ⁺ Methane-based compounds are mixed and used as a coloring agent. However, since the phthalocyanine-based pigment used in the above method is still a pigment not dissolved in a solvent, it is necessary to develop a new method for improving the solubility.

An object of the present invention is to provide a coloring dye for a color filter having a high luminance by improving the solubility in a solvent and moving the light absorbing region to a blue region by using a strong electron withdrawing group, and a method for producing the same.

Another object of the present invention is to provide a coloring dye suitable for use as a coloring dye for a color filter excellent in heat resistance, light resistance and chemical resistance.

It is still another object of the present invention to provide a photosensitive resin composition containing the above-mentioned colored dye.

The present invention provides a colored dye for a color filter represented by the following formula (1)

[Chemical Formula 1]

In Formula 1, R ₁ to R include at least one or more of the _4, wherein R ₁ to R ₄ each independently represent a hydrogen, an alkyl group, a Substituent of Formula 2 having 1 to 5 carbon atoms, the substituent of formula (3) , At least one of R ₁ to R ₄ is a substituent of the following formula (2), a substituent of the formula (3) or a substituent of the formula (2) and the formula (3)

p is an integer of 0 to 4, provided that p is not 0 at the same time,

M is Cu or Zn.

(2)

(Wherein Ar represents a hydrocarbon aromatic group or a heterocyclic aromatic group,

R ₅ is

, or

ego,

and t is an integer of 0 to 3)

(3)

(In the formula 3, L is -NH-, -NHCO-, -NHCS-, -S-, -SO 2 -, -CH-, -CH 2 - -O-, -CO-, or -CF ₂ - ego,

A is _{-CH 2 -, -CF 2 -,} -CO-, -CH 2 CH 2 O-, -SO 2 -, or

ego,

E is _{-CF 3, -CH 3, -SO 3} H, -NH 2, -OH, OCH 3, -SH, -C (CH 3) 3, -CH (CH 3) 2 or a halogen atom,

n and m are each independently an integer of 0 to 20)

The present invention also provides a photosensitive resin composition for a color filter comprising the above-mentioned dye.

The present invention provides a novel dye for a color filter excellent in solubility in a resin solution by substituting a cyanoacetic acid which is an organic functional group with a phthalocyanine pigment. In particular, the present invention relates to a method for introducing a substituent having a fastness to heat and light among organic functional groups, wherein a substituent is substituted for a cyanoacetic acid group, which is a strong electron withdrawing group, at the terminal of the phthalocyanine, To a short wavelength region, and at the same time, by introducing various electron confinement groups, an absorption wavelength band can be controlled and an excellent coloring dye having high luminance and high transmittance characteristics can be provided by effectively transmitting light in a certain region.

Moreover, the present invention can be used as an adjunct to supplement the disadvantages of pigments by adding the dye to a color pigment composition for a color filter. The dyes of the present invention can also be used as dyes for dye-sensitized solar cells or as pigment compositions for inks.

1 shows the results of the transmittance according to the wavelength region of the photosensitive composition of Example 1. Fig.
Fig. 2 shows the results of the transmittance according to the wavelength range of the photosensitive composition of Example 2. Fig.
Fig. 3 shows the results of the transmittance according to the wavelength region of the photosensitive composition of Example 3. Fig.
4 shows the results of the transmittance according to the wavelength range of the photosensitive composition of Comparative Example 1. Fig.

Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

Also, " comprising "as used herein should be interpreted as specifying the presence of particular features, integers, steps, operations, elements and / or components, It does not exclude the presence or addition of an ingredient.

Hereinafter, the low temperature curable photosensitive resin composition according to one preferred embodiment of the present invention will be described in more detail.

According to one embodiment of the present invention, there is provided a coloring dye for a color filter represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ to R include at least one or more of the _4, wherein R ₁ to R ₄ each independently represent a hydrogen, an alkyl group, a Substituent of Formula 2 having 1 to 5 carbon atoms, the substituent of formula (3) , At least one of R ₁ to R ₄ is a substituent of the following formula (2), a substituent of the formula (3) or a substituent of the formula (2) and the formula (3)

p is an integer of 0 to 4, provided that p is not 0 at the same time,

M is Cu or Zn.

(2)

(Wherein Ar represents a hydrocarbon aromatic group or a heterocyclic aromatic group,

R ₅ is

, or

ego,

and t is an integer of 0 to 3)

(3)

(In the formula 3, L is -NH-, -NHCO-, -NHCS-, -S-, -SO 2 -, -CH-, -CH 2 - -O-, -CO-, or -CF ₂ - ego,

A is _{-CH 2 -, -CF 2 -,} -CO-, -CH 2 CH 2 O-, -SO 2 -, or

ego,

E is _{-CF 3, -CH 3, -SO 3} H, -NH 2, -OH, OCH 3, -SH, -C (CH 3) 3, -CH (CH 3) 2 or a halogen atom,

n and m are each independently an integer of 0 to 20)

In the present invention, by introducing a cyanoacetic acid group or the like into phthalocyanine as a pigment for providing blue and green pixels, not only the solubility in the resin solution is excellent but also the absorption region due to the strong electron withdrawing group By moving to the short wavelength region and introducing the electron confinement group at the same time, it is possible to control the absorption wavelength band of such a dye by effectively transmitting the light of a certain region and thereby to obtain the dye having high brightness, high transmittance characteristic and excellent in fastness due to heat and light . The dye of formula (1) provided by the present invention may include a blue-based or a green-based coloring dye.

In addition, the coloring dye of the present invention can be used as a dye in a photosensitive resin composition and exhibits excellent effects in the production of a color filter.

Accordingly, the dyes synthesized in the present invention may be bluish or, in some cases, green dyes. If the dye has a blue color, a blue photosensitive resin composition can be prepared. If the dye is green, a green photosensitive resin composition can be prepared using a green pigment.

Hereinafter, the coloring dye of formula (1) of the present invention will be described in more detail.

As described above, the coloring dye of the present invention is a compound represented by the general formula (1) and has a tetraazaporphyrin structure in its structure. In Formula 1, at least one of R ₁ to R _{4 may} include a substituent of Formula 2, a substituent of Formula 3, or a substituent of Formula 2 and Formula 3.

Here, the formula 3 is a strong electron withdrawing group, maximizing the effect of moving the absorption region to a short wavelength, and improving the solubility due to the acid function of the acetic acid group. However, since the solubility of the compound of formula (3) is short due to the short substituent, solubility of the solvent may be improved by improving the solubility of the compound of formula (2). Accordingly, in the present invention, it is possible to include only the formula 3 of R ₁ to R ₄ in the formula (1), but it is more preferable to include the formula (2) in order to solve the solubility problem of the formula (3).

For example, according to a preferred embodiment of the present invention, at least one of R ₁ to R ₄ in Formula 1 may include the structure of Formula 2. However, all of R ₁ to R ₄ in the present specification do not include the structure of Formula 2, and in this case, the remaining substituents may include hydrogen or an alkyl group having 1 to 5 carbon atoms.

According to another preferred embodiment of the present invention, at least one of R ₁ to R ₄ in Formula 1 may include the structure of Formula (3). In this case, the remaining substituents may include hydrogen or an alkyl group having 1 to 5 carbon atoms.

Further, according to another embodiment preferred according to the present invention, the above formula 1, R ₁ to R at least one or more of the _four are at least one of, R ₁ to R ₄ the remaining substituents of when the structure of formula (II) of formula (3) Structure. Further, in the above formula 1, R ₁ to R at least one of the _four is when the structure of Formula 3, R ₁ to R ₄ at least one of the remaining substituents of the may have a structure of formula (2).

In the structure of the above formula (1), when at least one specific organic functional group substituent of the formula (2) or (3) is not contained, not only the solubility is lowered but also the wavelength shift is difficult.

In Formula 2, Ar may be any one selected from the following substituents.

In the above formula (3), n and m are each independently preferably an integer of 0 to 8.

In Formula 1, p is preferably an integer of 1 to 4, and more preferably 1 at p. In the above formula (1), when p is 1, the remaining substituents may be hydrogen or an alkyl group having 1 to 5 carbon atoms.

The formula 1 preferably includes any one selected from the following formulas.

The colored pigment of Formula 1 of the present invention may be prepared by modifying a substituent at the terminal of the phthalocyanine blue structure according to an organic synthesis method well known in the art.

In the meantime, the pigment of the formula (1) of the present invention can be synthesized by a general cyclization reaction to synthesize the structure of phthalocyanine blue, and then the substituent is modified at the terminal of the phthalocyanine blue.

It is preferable that at least one of the substituents includes at least one substituent of the above-described formula (2) or (3).

For example, the present invention relates to a process for producing a compound represented by the general formula (2) or (3) or a precursor compound derived from such a structure by using the phthalonitrile of the general formula (a) as a starting material, (2) or (3) to produce a phthalocyanine dye having a tetraazaporphyrin structure of formula (1) through a series of steps, .

(A)

(Wherein A is an amino group or a halogen)

The metal-containing acetate compound is preferably copper acetate or zinc acetate.

The halogen-substituted aromatic compound may include at least one hydrocarbon aromatic group or heterocyclic aromatic group having an aryl group having 6 to 20 carbon atoms.

The preparation of the compound of formula (1) according to one preferred embodiment of the present invention can be carried out according to the following reaction formulas (1) to (5).

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

[Reaction Scheme 4]

[Reaction Scheme 5]

In Schemes 1 and 2, compounds b and c are prepared by reacting phthalonitrile (compound a) having an amino substituent group with a compound having a substituent structure of the formulas 2 and 3, respectively.

Then, the compounds b and c are reacted with copper acetate and 1-chloronaphthalene to prepare an intermediate compound d having a phthalocyanine structure and containing substituent structures of the formulas (2) and (3) at the aromatic ring end. (Scheme 3)

Further, a method in which a cyano group contained in the terminal of the phthalocyanine of the intermediate compound d is replaced with an aldehyde group using a catalyst to prepare an intermediate compound e (Scheme 4), and then the intermediate compound e is substituted with a substituent derived from cyanoacetic acid 5), the compound of formula (1) can be prepared.

According to another embodiment of the present invention, there is provided a photosensitive resin composition for a color filter comprising the colored dye.

The coloring dye of Formula 1 is preferably contained in an amount of 0.5 to 80 parts by weight, more preferably 0.5 to 60 parts by weight, and most preferably 0.5 to 50 parts by weight based on 100 parts by weight of the binder resin added to the photosensitive resin composition. If the amount of the coloring dye used is less than 0.5 parts by weight, the light absorbing region can not be moved to the blue region, so that a high brightness can not be realized. Also, since the concentration is low, a sufficient transmittance can not be realized. If the content exceeds 80 parts by weight, discoloration or color change occurs at a post-process at a high temperature, and foreign matter may be generated upon formation of a colored layer due to lack of compatibility with a material.

In addition, the photosensitive resin composition of the present invention may further contain an organic or inorganic pigment well known in the art, in addition to the pigment of the above formula (1).

Specific examples of such organic pigments include C.I. # 177, # 202, # 209, # 242, # 254, # 255; As the yellow pigment, C.I. # 150, # 138, # 128 C.I. # 43; C.I. # 7, # 36, # 58; C.I. # 15, # 15: 3, # 15: 6; As a violet pigment, C.I. # 23; C.I. # 1, # 7; and so on. Examples of the inorganic pigments include titanium oxide, titanium black, and carbon black. These pigments may be used alone or in combination of two or more thereof in order to make color combinations.

Further, the present invention may further include an auxiliary dye. These auxiliary dyes may be at least one selected from the group consisting of an azo dye, an anthraquinone dye, an indigo dye, a xanthine dye, a triphenylmethane dye, a phthalocyanine dye, an imine dye, and a quinapthanone dye compound.

Also, in the present invention, when the dye is added to the photosensitive resin composition, it may be directly added to itself, or may be added in the form of a dispersion containing a dispersant, a solvent, or the like.

As the solvent that can be included in the dye dispersion composition, 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. At this time, it is preferable that the content of the solvent is adjusted so that the solid content of the dye dispersion becomes 5 to 30% by weight.

On the other hand, the photosensitive resin composition of the present invention may further comprise an alkali-soluble binder resin, a polymerization initiator, and a solvent. In addition, the present invention may further include a photo-crosslinking agent, a thermosetting agent, an additive, and the like, which are well known in the art, if necessary.

As the alkali-soluble binder resin, a polymerization initiator, a solvent and the like, materials well known in the art may be used, and the kind thereof is not particularly limited.

The binder resin is a component that secures dispersion stability of pigments and dyes to be described later, and allows pixels having a desired resolution to be formed in a developing process.

For example, the alkali-soluble binder resin may be a copolymer of a monomer having at least one ethylenic acid group and at least one (meth) acrylate monomer. The binder resin preferably comprises 10 to 40% by weight of a monomer having an ethylenic acid group and 60 to 90% by weight of a (meth) acrylate monomer, preferably 20 to 40% by weight of a monomer having an ethylenic acid group and a (meth) And 60 to 80% by weight of the monomer, more preferably 25 to 35% by weight of the monomer having an ethylenic acid group and 65 to 75% by weight of the (meth) acrylate monomer.

Such a binder resin may be contained in an amount of 5 to 70% by weight based on the total weight of the composition. That is, it is preferable that the binder resin is contained in an amount of 5 wt% or more in order to exhibit the minimum dispersion stability, film strength, heat resistance, etc. upon addition of the binder resin. When the binder resin is used in an excessive amount, the viscosity of the composition may be increased excessively, thereby deteriorating the optical properties, physical properties, and process efficiency of the composition. To prevent such a phenomenon, .

The polymerization initiator may be selected from the group consisting of acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, and mixtures thereof.

The content of the polymerization initiator can sufficiently induce the polymerization reaction and can be determined in consideration of the phenomenon of the decrease in the transmittance due to the unreacted initiator after the polymerization. According to the present invention, the content of the polymerization initiator may be 5 to 50 parts by weight, preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the binder resin.

The solvent is added to control the solubility and viscosity of the components contained in the composition. Any solvent that is compatible with the above-described components may be used without limitation, have.

The solvent may be used as the balance relative to the total weight of the entire photosensitive resin composition, and the range is not particularly limited.

According to an embodiment of the present invention, the solvent may be at least one selected from the group consisting of alcohols such as methanol, ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol diacetone alcohol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as 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 ethyl acetate, 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 esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketonic acid esters such as ethyl pyruvate; Or a mixture thereof.

In addition, the solvent may be selected from the group consisting of N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, , Gamma-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, ethylene glycol acetate, ethyl cellosolve, ethyl lactate, polyethylene glycol and the like.

The photosensitive resin composition of the present invention may further include other additives well known in the art. The additive may be an epoxy compound, malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a silicon or fluorine leveling agent, a surfactant, and the like. The content of such additives is not particularly limited as it can be determined according to the properties to be controlled within a range not adversely affecting the physical properties of the composition.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

 [ Synthesis Example 1 ]

A copper phthalocyanine dye (Formula 1) having one structure derived from cyanoacetic acid was substituted according to the following Reaction Schemes 1 to 5.

1. Synthesis of benzene-1,2,3-tricarbonitrile (Compound b)

[Reaction Scheme 1]

To 9 mL of water were mixed 1 mL of acetic acid and 4-aminophthalonitrile (a) (3.0 g, 20.95 mmol), and sulfuric acid (12 g, 122.35 mmol) was slowly dropped thereon. The mixture was stirred slowly and then cooled to 0 < 0 > C when completely dissolved. Sodium nitrite (NaNO ₂ ) (1.8 g, 26.09 mmol) was dissolved in 3 mL of water, slowly dropped into the mixture over 30 minutes, and stirred for 30 minutes.

After preparing the different reaction vessel Copper sulfate pentahydrate _{(CuSO 4? 5H 2 O)} (6.3 g, 25.23 mmol) was dissolved in water 16 mL lower the temperature of the reactor to 0 ℃, potassium among cyanide (KCN) (6.5 g, 99.82 mmol) was dissolved in 16 mL of water. 14 g of sodium bicarbonate (NaHCO ₃ ) and 14 mL of toluene were added. The thus-prepared mixture was slowly dropped into the above-prepared azonium-salt-added reactor over 30 minutes, then heated to 50 DEG C and stirred for 3 hours. After the completion of the reaction, 100 mL of toluene and water were added to extract, followed by drying with anhydrous Na ₂ SO ₄ , followed by filtration and concentration. The mixture was separated by flash column chromatography (Hexane: EtOAc = 4: 1) under SiO ₂ to obtain 0.32 g (20% yield) of compound (b). The synthesized compound was confirmed by ¹ H-NMR.

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 8.78 (1H, d, J = 1.2 Hz), 8.45-8.43 (1H, dd, J = 8.4 Hz), 8.38-8.36 (1H, d, J = 8 Hz)

2. Synthesis of N- (3,4-dicyanophenyl) octane-1-sulfonamide (Compound c)

[Reaction Scheme 2]

4-aminophthalonitrile (a) (10.0 g, 69.85 mmol) and pyridine (130 mL) were mixed together and completely dissolved at room temperature. Octanesulfonyl chloride (27.49 g, 129.22 mmol) was slowly added dropwise and stirred for 1 hour.

200 mL of ice was added to the beaker, and the mixture was poured to terminate the reaction. After extraction with 200 mL of EtOAc and water, the mixture was dried with anhydrous Na ₂ SO ₄ , filtered, and concentrated. The mixture was separated by flash column chromatography (Hexane: EtOAc = 3: 1) under SiO ₂ to obtain 10.3 g (46% yield) of compound (c). The synthesized compound was confirmed by ¹ H-NMR.

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 7.77-7.75 (1H, d, J = 8.4 Hz), 7.59-7.59 (1H, d, J = 2.4 Hz), 7.47-7.54 (1H, d, J = 8.4 Hz), 6.90 (1H, s), 3.23-3.19 (2H, t, J = 8 Hz), 1.87-1.81 (2H, q, J = 8 Hz), 1.44-1.25 0.89-0.86 (3H, t, J = 7.2 Hz

3. Synthesis of compound d

[Reaction Scheme 3]

Compound (b) (0.36 g, 2.35 mmol) and compound (c) (3 g, 9.39 mmol) were mixed with 30 mL of 1-chloronaphthalene, To room temperature. Then, the mixture was added with capper acetate (Cu (CH ₃ COO) ₂ ) (0.78 g, 4.32 mmol), and the temperature was then raised to 250 ° C. and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was filtered and washed several times with EtOAc solvent. The filtrate was concentrated and separated by flash column chromatography under SiO ₂ to obtain 0.3 g (11% yield) of compound (d). The synthesized compound was confirmed by ¹ H-NMR.

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 7.89-6.68 (12H, m), 6.90 (3H, s), 3.42-3.12 (6H, t, J = 8 Hz), 1.88-1.20 (36H, m), 0.86-0.83 (9H, t, J = 7.2 Hz)

4. Synthesis of Compound e

[Reaction Scheme 4]

Compound (d) (0.3 g, 0.26 mmol) was dissolved in 30 mL of anhydrous benzene, and diisobutyl aluminum hydride (DIBAL-H) (0.05 mL, 0.29 mmol) dissolved in 1M hexene was added thereto. The mixture was stirred at room temperature under nitrogen for 6 hours. After completion of the reaction, 50 mL of 10% sulfuric acid was added, and benzene was added thereto. The mixture was extracted, washed with brine, dried with anhydrous Na ₂ SO ₄ , filtered and concentrated. The mixture was separated by flash column chromatography method under SiO ₂ to obtain 0.2 g (65% yield) of compound (e). The synthesized compound was confirmed by ¹ H-NMR.

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 9.88 (1H, s), 7.89-6.92 (12H, m), 6.88 (3H, s), 3.15 (6H, t, J = 8 Hz), 1.61 -1.29 (36H, m), 0.86-0.83 (9H, s, J = 7.2 Hz)

5. Synthesis of Compound 1

[Reaction Scheme 5]

 2-cyanoacetic acid (0.057 g, 0.68 mmol) and piperidine (4 mL) were added to a solution of compound (e) (0.2 g, 0.17 mmol) mL. And the mixture was stirred at 80 DEG C for 4 hours under nitrogen filling. After the reaction is completed, the temperature is lowered to room temperature and the organic layer is removed by decompression.

The precipitate was filtered off and the mixture was flash column chromatography (flash column chromatography) under the SiO ₂ washed with distilled water _{(EtOH: CH 2 Cl 2 =} 1: 1) , separated by a method of the compound (2) 0.1 g (48% yield ).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 11.20 (1H, s), 7.95 (1H, s), 7.89-6.92 (12H, m), 6.88 (3H, s), 3.15 (6H, t, J = 8 Hz), 1.61-1.29 (36H, m), 0.86-0.83 (9H, s, J = 7.2 Hz)

[ Synthetic example  2]

6. Synthesis of Compound f

[Reaction Scheme 6]

4-aminophthalonitrile (a) (3.0 g, 20.96 mmol) and pyridine (32 mL) were mixed together and completely dissolved at room temperature. Trimethylacetyl chloride (3.54 g, 29.34 mmol) was slowly added dropwise and stirred for 1 hour.

70 mL of ice was added to the beaker, and the mixture was poured to terminate the reaction. Extracted with 70 mL of EtOAc, washed with brine, dried with anhydrous Na ₂ SO ₄ , filtered, and concentrated. The mixture was separated by flash column chromatography (Hexane: EtOAc = 3: 1) under SiO ₂ to obtain 10.3 g (46% yield) of compound (c).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 8.19-8.18 (1H, d, J = 2.4 Hz), 7.89-7.86 (1H, dd, J = 8.4 Hz), 7.75-7.73 (1H, d, J = 8.4 Hz), 7.60 (1H, s), 1.34 (3H, s)

7. Synthesis of Compound g

[Reaction Scheme 7]

4-aminophthalonitrile (a) (3.0 g, 20.96 mmol) was dissolved in 42 ml of 2M sulfuric acid (H ₂ SO ₄ ) and the temperature was lowered to 0 ° C. Sodium nitrite (NaNO ₂ ) (1.93 g, 3.94 mmol) was dissolved in 55 mL of water, and the mixture was slowly dropped into the mixture over 30 minutes while maintaining the temperature at 0 ° C, followed by stirring for 30 minutes . The mixture is decompressed, and the mixture obtained by dissolving 210 ml of water and potassium iodide (KI) (3.72 g, 22.42 mmol) in a reduced pressure mixed solution is gradually dropped.

The mixture is slowly stirred at room temperature and stirred, and the precipitated mixture is reduced in pressure to obtain a solid precipitate. The solid precipitate thus obtained was dissolved in dichloromethane (CH ₂ Cl ₂ ), washed with 5% sodium bicarbonate (NaHCO ₃ ), dried with anhydrous Na ₂ SO ₄ , filtered, and concentrated. The mixture was separated by flash column chromatography (MC) method under SiO ₂ to obtain 2.9 g (59% yield) of compound (g).

¹ H-NMR (CDCl ₃ , Varian 400 MHz):? 8.17-8.16 (IH, d, J = 1.2 Hz), 8.12-8.10 (IH, d, J = 8.4 Hz), 7.52-7.50 J = 8.4 Hz)

8. Synthesis of Compound h

[Reaction Scheme 8]

Compound (f) (3.0 g, 12.20 mmol) and compound (g) (0.71 g, 3.05 mmol) were mixed with 30 mL of 1-chloronaphthalene, To room temperature. Then, the mixture was added with capper acetate (Cu (CH ₃ COO) ₂ ) (0.78 g, 4.32 mmol), and the temperature was then raised to 250 ° C. and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was filtered and washed several times with EtOAc solvent. The filtrate was concentrated and separated by flash column chromatography under SiO ₂ to obtain 0.5 g (16% yield) of compound (h).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 7.89-6.68 (12H, m), 6.90 (3H, s), 3.42-3.12 (6H, t, J = 8 Hz), 1.88-1.20 (36H, m), 0.86-0.83 (9H, t, J = 7.2 Hz)

9. Synthesis of Compound j

[Reaction Scheme 9]

Compound (h) (1.0 g, 1.00 mmol), 5-formylthiophene-2-ylboronic acid (i) (0.16 g, 1.00 mmol), tetrakispalladium tri phenyl Posey pin _{(Pd (PPh 3) 4)} (0.015 g, 0.013 mmol), potassium carbonate (potassium carbonate) (2.60 g, 18.80 mmol) was dissolved in 2 mL of toluene 20 mL and water at 110 ℃ for 24 hours Followed by stirring.

After completion of the reaction, the reaction mixture was extracted and extracted with 70 mL of EtOAc, washed with brine, dried with anhydrous Na ₂ SO ₄ , filtered and concentrated. The mixture was separated by flash column chromatography method under SiO ₂ to obtain 0.7 g (71% yield) of compound (j).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 9.84 (H, s), 8.45-7.48 (14H, m), 7.03 (3H, s), 1.85-1.23 (27H, m)

10. Synthesis of Compound 2

[Reaction Scheme 10]

2-cyanoacetic acid (0.035 g, 4.08 mmol) and piperidine (2 mL, 20.4 mmol) were added to a solution of compound (j) (1 g, 1.02 mmol) in acetonitrile ). ≪ / RTI > And the mixture was stirred at 80 DEG C for 4 hours under nitrogen filling. After the reaction was completed, the temperature was lowered to room temperature and the organic layer was removed under reduced pressure.

The precipitate was filtered off and the mixture was flash column chromatography (flash column chromatography) under the SiO ₂ washed with distilled water _{(EtOH: CH 2 Cl 2 =} 1: 1) separated by the method to the compound (2) 0.75 g (70% yield ).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 11.0 (1H, s), 8.35-7.92 (14H, m), 7.23 (3H, s), 1.85-1.23 (27H, m)

[ Synthetic example  3]

11. Synthesis of Compound k

[Reaction Scheme 11]

4-iodophthalonitrile (f) (15 g, 59.05 mmol) and 4-methoxyphenylboronic acid (k) (13.46 g, 88.58 mmol) , palladium triphenyl Posey pin _{(Pd (PPh 3) 4)} (3.41 g, 2.95 mmol), potassium carbonate (potassium carbonate) (26.93 g, 194.87 mmol) was dissolved in 2 mL of toluene 18 mL and water for 24 hours Followed by stirring at 110 ° C.

After completion of the reaction, the reaction mixture was extracted and extracted with 70 mL of EtOAc, washed with brine, dried with anhydrous Na ₂ SO ₄ , filtered and concentrated. The mixture was separated by flash column chromatography method under SiO ₂ to obtain 8.0 g (캜 58% yield) of compound (k).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ 7.97 (1H, s), 7.89-7.87 (1H, dd, J = 8 Hz), 7.84-7.82 (1H, d, J = 8.4 Hz), 7.55 (2H, d, J = 8.8 Hz), 3.88 (3H, s), 7.05-7.53

12. Synthesis of Compound 3

[Reaction Scheme 12]

Compound (k) (3 g, 11.80 mmol) was mixed with 30 mL of 1-Chloronaphthalene, and the temperature was raised to 250 DEG C for 30 minutes, and then the temperature was dropped to room temperature. Then, the mixture was added with capper acetate (Cu (CH ₃ COO) ₂ ) (0.78 g, 4.32 mmol), and the temperature was then raised to 250 ° C. and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was filtered and washed several times with EtOAc solvent. The filtrate was concentrated and separated by flash column chromatography under SiO ₂ to obtain 1.5 g (13% yield) of the compound (3).

_{^{1 H-NMR (CDCl 3,}} Varian 400 MHz): δ8.16-7.68 (20H, m), 7.05 (8H, dd, J = 8.4 Hz), 3.83 (12H, s)

[Example 1]

Using the dye of Synthesis Example 1, a photosensitive resin composition was prepared by a general method.

That is, 30% Ethyl-L-lactate solution of a binder resin (water-soluble acrylic polymer; benzyl methacrylate / methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio [molar ratio] = 60:30:10), E34102, Aldrich ), About 180 parts by weight of a reactive unsaturated compound (a mixture of about 60 parts by weight of a bisphenol epoxy acrylate oligomer and about 120 parts by weight of dipentaerythritol hexaacrylate) 10 parts by weight of the blue dye dispersion of Synthesis Example 1 (10% by weight of the dye of Synthesis Example 1 dispersed in propylene glycol monoethyl ether acetate as a solvent) 50 parts by weight of a blue pigment dispersion (trade name: DJBLUE-01, manufactured by MIKYNI, solvent: propylene glycol methyl ether acetate, about 15% by weight of pigment as a dispersion and about 93.75 parts by weight in terms of pigment content), a photopolymerization initiator (trade name: Irgacure- Manufactured by BASF)), 52 parts by weight of propylene glycol methyl ether acetate as a solvent; And 0.01 part by weight of a fluorine leveling agent (trade name: F-474, manufacturer: DIC) were mixed and stirred at room temperature for about 2 hours, and then the impurities were removed through a 1.2 占 퐉 filter.

[Example 2]

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the dye of Synthesis Example 2 was used.

[Example 3]

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the dye of Synthesis Example 3 was used and a green pigment dispersion (CI Pigment Green 58) was used.

[Comparative Example 1]

A photosensitive resin composition was prepared in the same manner as in Example 1, except that CI acid blue 25 (trade name: Acid blue 25 (manufacturer: ALDRICH)) was used instead of the dye of Synthesis Example 1.

[evaluation]

Each of the photosensitive resin compositions according to Examples 1 to 3 and Comparative Example 1 was spin-coated on a glass substrate (10 X 10 cm) to a thickness of 2 탆 and pre-baked on a 90 ° hot plate for 2 minutes. bake), followed by cooling at room temperature for 1 minute. This was exposed using an exposure apparatus at an exposure dose of 100 mJ / cm 2 (365 nm standard), and then post-baked for about 30 minutes in a 220 ° ventilated oven.

The physical properties of each of the samples prepared as described above were measured as follows.

(Heat resistance measurement)

The post-baked substrate was heated in an oven at about 240 DEG C for about 30 minutes, and then the chromaticity change on the pattern image before and after irradiation, that is, the color difference (DELTA Eab) was measured using a color meter MCPD- ) Were measured. The heat resistance results of the dyes used in Synthesis Examples 1 to 3 and Comparative Example 1 are shown in Table 1 according to the following criteria.

Criteria

○: ΔEab value <5

?:? Eab value? 10

Ⅹ: 10 <△ Eab value

(Solubility evaluation)

The solubilities of the dyes of Synthesis Examples 1 to 3 and Comparative Example 1 were measured using PGMEA, PGME, EL and DMAc as solvents, and the results are shown in Table 1 below. In the following table, solubility of 10% or more is indicated by o, solubility of 2% to 10% is indicated by △, solubility of less than 2% is indicated by Ⅹ, and it is shown in Table 2.

PGMEA: Propylene glycol monoethyl ether acetate

PGME: Propylene glycol monoethyl ether

EL: ethyl lactate

DMAc: Dimethylacetamide

Color filter Heat resistance (? Eab) Example 1 Blue ○ Example 2 Blue △ Example 3 Green ○ Comparative Example 1 Blue ○

PGMEA PGME EL DMAc Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 △ △ ○ ○ Comparative Example 1 △ △ △ X

As shown in Tables 1 and 2, the solubility and heat resistance of the dyes of Examples 1 to 3 of the present invention were superior to those of Comparative Example 1.

(Measurement of transmittance by wavelength region for color filter)

The transmittance of each of the color filter samples prepared by using the compositions according to Examples 1 to 3 and Comparative Example 1 was measured using a chromaticity meter (manufacturer: Otsuka, model name: MCPD-3000) , And the results are shown in Figs. At this time, the maximum transmittance (Max%) of blue light in the wavelength region of 450 to 460 nm and green light in the wavelength region of 515 to 550 nm was measured.

As a result, Examples 1 to 3 (Figs. 1 to 3) had better transmittance than Comparative Example 1 (Fig. 4).

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (11)

A colored dye for a color filter represented by the following formula (1)
[Chemical Formula 1]

In Formula 1, R ₁ to R include at least one or more of the _4, wherein R ₁ to R ₄ each independently represent a hydrogen, an alkyl group, a Substituent of Formula 2 having 1 to 5 carbon atoms, the substituent of formula (3) , At least one of R ₁ to R ₄ is a substituent of the following formula (2), a substituent of the formula (3) or a substituent of the formula (2) and the formula (3)
p is an integer of 0 to 4, provided that p is not 0 at the same time,
M is Cu or Zn.
(2)

(Wherein Ar represents a hydrocarbon aromatic group or a heterocyclic aromatic group,
R ₅ is

, or

ego,
and t is an integer of 0 to 3)
(3)

(In the formula 3, L is -NH-, -NHCO-, -NHCS-, -S-, -SO 2 -, -CH-, -CH 2 - -O-, -CO-, or -CF ₂ - ego,
A is _{-CH 2 -, -CF 2 -,} -CO-, -CH 2 CH 2 O-, -SO 2 -, or

ego,
E is _{-CF 3, -CH 3, -SO 3} H, -NH 2, -OH, OCH 3, -SH, -C (CH 3) 3, -CH (CH 3) 2 or a halogen atom,
n and m are each independently an integer of 0 to 20)
The method according to claim 1,
In the formula (1), at least one of R ₁ to R ₄ includes the structure of formula (2).
In the formula (1), at least one of R ₁ to R ₄ includes the structure of formula (3).
The method according to claim 1,
In Formula _1, R 1 to R ₄ of when the at least the at least one structure represented by the following formula 2, R ₁ to R ₄ of the color filter for the colored dye is at least one of the remaining substituents have a structure of formula (3).
The method according to claim 1,
In Formula _1, R 1 to R ₄ of when the at least the at least one structure represented by the following formula 3, R ₁ to R ₄ of the color filter for the colored dye is at least one of the remaining substituents have a structure of formula (2).
The coloring dye for a color filter according to claim 1, wherein Ar in formula (2) is any one of the following substituents.

The method according to claim 1,
In the formula (3), n and m are each independently an integer of from 0 to 8.
The method according to claim 1,
In the above formula (1), when p is 1, the remaining substituent is hydrogen or an alkyl group having 1 to 5 carbon atoms.
The coloring dye for a color filter according to claim 1, wherein the formula (1) comprises any one selected from the following formulas.

10. A photosensitive resin composition for a color filter comprising the coloring dye according to any one of claims 1 to 9.
The photosensitive resin composition for a color filter according to claim 10, further comprising an alkali-soluble resin, a polymerization initiator and a solvent.

Images