KR101828935B1 - Novel compound, blue resin composition for color filter including the same, and color filter using the same - Google Patents

Abstract

The present invention relates to a compound in the form of a dimer, a blue resin composition for a color filter comprising the same, and a color filter using the same, wherein the compound is a triarylmethane compound having excellent solubility and thermal stability and a wide transmittance wavelength, It is possible to provide a blue resin composition for a color filter excellent in heat resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, a blue resin composition for a color filter comprising the same, and a color filter using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel compound having improved solubility and thermal stability, a blue resin composition for a color filter comprising the same, and a color filter using the same.

A color filter is used for realizing color in a liquid crystal display device. The color filter is a unit in which subpixels of three primary colors of red (R), green (G), and blue (B) And pixels are repeatedly formed.

As a method of manufacturing such a color filter, a pigment dispersion method using a pigment excellent in thermal stability, light resistance, chemical resistance, and the like has been used. However, when such a pigment dispersion method is used, scattering of light occurs due to agglomeration phenomenon of the pigment, so that it is difficult to realize a color filter having high brightness and high resolution. Further, since the development and washing processes must be repeated during the dispersion process of the pigment, the generation of the waste solution is increased, and it is not economical and it is difficult to manufacture the color filter in an environmentally friendly manner.

Accordingly, a dye-based color filter capable of producing color filters of various sizes by a simple process without the phenomenon of agglomeration of pigments and without scattering of light and applying a dyeing method or an ink jet method Interest in the process is growing.

However, the dyes have poor heat stability, light resistance, and chemical resistance, which are indispensable properties for achieving high brightness, high resolution and high contrast ratio of the color filter as compared with the pigment, and problems are encountered in realizing color fillers using dyes.

As a method to solve this problem, triarylmethane dyes, one of the cationic dyes, are under study. These triarylmethane dyes have high transmittance at a wavelength of 420 nm to 450 nm, excellent light resistance, and are effective in improving the luminance and contrast ratio of color filters. However, it has a low solubility in propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and the like, which are solvents mainly used for color filter compositions for coloring blue, and is poor in heat resistance, have.

As a result of intensive efforts, the inventors of the present invention have found that, when a triarylmethane compound is synthesized in the form of a dimer and the anion is substituted in the synthesized compound, a compound having improved solubility and thermal stability can be prepared And confirmed the present invention.

The present invention is to provide a novel compound with improved solubility and thermal stability.

The present invention also provides a blue resin composition for a color filter comprising the above compound.

The present invention also provides a color filter using the blue resin composition for a color filter.

In order to solve the above problems, the present invention provides a compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

The rings A ₁ and A ₂ are each independently benzene or naphthalene,

n is an integer of 1 to 100,

R ₁ to R ₈ are each independently hydrogen, C _1-20 alkyl, C _6-20 aryl, or - (CH ₂ ) _m -OC (═O) -CH (Q ₁ ) (Q ₂ )

Wherein C _1-20 alkyl and C _6-20 aryl are each independently unsubstituted or substituted by one or more groups independently selected from the group consisting of halogen, hydroxy, C _1-5 alkyl and C _1-5 alkoxy, or Substituted by two substituents,

m is an integer from 1 to 3, Q ₁ and Q ₂ are each independently hydrogen or C _1-10 alkyl,

R ₁₁ to R ₁₆ are each independently hydrogen, halogen, hydroxy, C _1-5 alkyl, or C _1-5 alkoxy,

a1 and a2 are each independently an integer of 0 to 6,

a3 to a6 each independently represent an integer of 0 to 4,

X is halogen, bis (trifluoromethane) sulfonimide, or trifluoromethanesulfonate.

The compound represented by the formula (1) is a triarylmethane compound having two triarylmethane derivatives having three aryl groups around the central carbon, which are connected by ethylene oxide, and two nitrogen atoms having an intramolecular positive charge It corresponds to a salt that is ionically bonded to two anions.

Accordingly, the compound represented by the formula (1) can control the solubility and the transmission wavelength by changing the number of the ethylene oxide or the type of the anion serving as a linker.

Specifically, the A ₁ and A ₂ rings may be the same as each other. In this case, the compound represented by Formula 1 may have a dimer form.

For example, the A ₁ and A ₂ rings may all be naphthalene. In this case, it may be advantageous in terms of thermal characteristics.

In the above formula (1), n represents the number of ethylene oxide. For example, n may be an integer of 1 to 50, or an integer of 1 to 20.

(CH ₂ ) _m -OC (═O) -CH (Q ₁ ) (Q ₂ ), wherein R ₁ to R ₈ are each independently selected from the group consisting of hydrogen, C _1-10 alkyl, C _6-10 aryl, ), Wherein m is 1 or 2, and Q ₁ and Q ₂ are each independently C _1-5 alkyl.

For example, R ₁ to R ₈ are each independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl, tert- butyl, or _{- (CH 2) 2 -OC (} = O) -CH (Q ₁ ) (Q ₂ ) wherein Q ₁ and Q ₂ are each independently hydrogen, methyl, ethyl, propyl, or butyl.

Here, R ₁ to R ₈ may be the same as each other. Therefore, all four nitrogen atoms capable of substituent bonding in a molecule may have the same substituent attached thereto.

In Formula 1, R ₁₁ to R ₁₆ each independently may be hydrogen, halogen, methyl, or methoxy. For example, R ₁₁ to R ₁₆ may all be hydrogen.

In the general formula (1), by a1 to a6 refers to the number of the substituents R ₁₁ to R ₁₆ each, for example, a1 to a6 can be each independently 0, 1 or 2;

In the above formula (1), X may be chloride or bis (trifluoromethane) sulfonimide. At this time, use of bis (trifluoromethane) sulfonimide is preferable in terms of solubility and improvement of thermal stability.

The compound represented by Formula 1 is advantageous in terms of thermal stability when the weight average molecular weight is 1,000 to 10,000 g / mol. Specifically, the compound represented by Formula 1 may have a weight average molecular weight of 1,000 to 6,000 g / mol. Particularly, a compound having a weight average molecular weight in the range of 1,000 to 4,000 g / mol is suitable for use as a resin composition for a color filter.

According to one embodiment, the compound may be represented by the following formula 1-1:

[Formula 1-1]

In Formula 1-1,

n and R ₁ to R ₈ are as defined above.

Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas:

[Formula V]

[Formula V-BTFI]

(VI)

[Formula VI-BTFI]

In the above Formulas V, V-BTFI, VI and VI-BTFI, n is an integer of 1 to 100.

On the other hand, the compound represented by Formula 1 may exhibit a transmittance in the range of 420 nm to 540 nm. Accordingly, the compound can be used as a blue dye. The transmission wavelength of the compound can be controlled by varying the number of ethylene oxides. Specifically, as the number of ethylene oxide in the compound increases, the range of the transmission wavelength may be widened.

The compound represented by Formula 1 may have a solubility (25) of 3 (g / 100 g solvent) or more with respect to a solvent of a blue resin composition for a color filter to be described later. For example, the solubility (25) for propylene glycol monomethyl ether acetate (PGMEA) solvent is preferably 3 (g / 100 g solvent) or more, specifically 3 to 20 g / 100 g solvent, or 3 to 15 g / 100 g solvent), so that the color filter can be easily manufactured by an ink jet process.

The compound represented by Formula 1-1 may be prepared, for example, according to the following Reaction Scheme 1:

[Reaction Scheme 1]

In the above Reaction Scheme 1, n, R ₁ to R ₄ and X are as defined above.

Step 1 is a step of reacting the compound represented by Formula 2 with p-toluenesulfonyl chloride to prepare a compound represented by Formula 3, wherein both ends of the glycol compound are reacted with p- Lt; / RTI > The reaction can be carried out at room temperature using a base such as sodium hydroxide, triethylamine or the like.

Step 2 is a step of reacting the compound represented by Formula 3 with 1-naphthylamine to aminate the compound of Formula 4. The amination reaction may be carried out at a temperature of about 50 DEG C to 200 DEG C for 3 to 7 days.

Step 3 is a step of reacting a compound represented by Formula 4 with a compound represented by Formula 5 to prepare a compound represented by Formula 1-1. At this time, a compound such as phosphorus oxyhalide may be added to prepare a salt-type compound into which a halogen anion is introduced. The reaction may be carried out in an organic solvent such as toluene, methylene chloride or the like for 1 to 48 hours.

On the other hand, after the step 3, an additional reaction can be carried out for the salt exchange. For example, in order to exchange a halogen anion in the compound with a bis (trifluoromethane) sulfonimide anion, the compound prepared in step 3 can be reacted with a bis (trifluoromethane) sulfonimide lithium salt And the reaction can be carried out in an alcohol solvent such as methanol, ethanol, tert-butanol and the like for 1 to 48 hours.

In the above production process, only the cases where the A ₁ and A ₂ rings in the formula (1) are naphthalene have been exemplarily described, but it is possible to prepare the compounds to be prepared by appropriately substituting the starting materials with reference to the structures of the reaction formulas 1 and .

On the other hand, the present invention provides a blue resin composition for a color filter comprising the above-mentioned compound as a dye.

The resin composition may further contain additional dyes, a binder resin, a reactive unsaturated compound, a polymerization initiator, and a solvent in addition to the compound represented by the formula (1).

The dyes which can be used together with the triarylmethane dyes represented by the above formula (1) include xanthene dyes, azapopyrine dyes and cyanine dyes generally used for a blue resin composition for a color filter. It is not.

On the other hand, the binder resin is used for enhancing the stability of the composition by imparting a binding force between the components, and generally, any resin used for a resin composition for a color filter can be used without limitation.

For example, the binder resin may be a cellulose resin, an acrylic resin, an alkyd resin, a melamine resin, an epoxy resin, a polyvinyl alcohol, a polyamide, a polyamide-imine, or a polyimide. Particularly, homopolymers and copolymers of polymerizable monomers, for example, aromatic vinyl compounds such as styrene,? -Methylstyrene, vinyltoluene and 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; Or an unsaturated amide compound such as (meth) acrylamide are useful. Particularly, an acrylic resin capable of photopolymerization is preferable.

Examples of such acrylic resins include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer , Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, 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 acrylic resin may be 3,000 to 150,000 g / mol, specifically 5,000 to 50,000 g / mol, and more specifically 20,000 to 30,000 g / mol. When the weight average molecular weight of the acrylic resin is in the range described above, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity of the composition may be suitable for coating.

The acid value of the acrylic resin may be 15 to 60 mgKOH / g, and specifically 20 to 50 mgKOH / g. When the acid value of the acrylic resin is within the above range, the resolution of the pixel can be excellent.

The acrylic resin is preferably used in an amount of 　 0.1 to 30% by weight, and specifically, 　 5 to 20% by weight. When the acrylic 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, whereby excellent surface smoothness can be obtained.

On the other hand, the reactive unsaturated compound may be a thermosetting monomer or an oligomer thereof, a photo-curable monomer or an oligomer thereof, or a combination thereof. Specifically, a photo-curable monomer containing at least one double bond in a molecule may be preferred.

Examples of the photocurable monomer include glycerol acrylate, dipentaerythritol hexaacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate , Neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol acrylate, pentaerythritol hexaacrylate , Bisphenol A diacrylate, trimethylolpropane triacrylate, novolak epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Agent, or it can be a combination thereof, but is not limited to this.

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

On the other hand, the polymerization initiator may be a thermal curing initiator, a photopolymerization initiator, or a combination thereof. For example, a photopolymerization initiator such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, a oxime-based compound, or a combination thereof may be mainly used.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, 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- Orcanthon and the like can be used.

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 type compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s- triazine, 2- (3 ', 4'-dimethoxy (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis 6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like can be used.

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

In addition to the above-described photopolymerization initiators, carbazole-based compounds, diketone compounds, sulfonium borate compounds, diazo compounds, and imidazole-based compounds can also be used as a photopolymerization initiator.

The polymerization initiator may be contained in an amount of 0.1 to 5% by weight based on the total amount of the blue resin composition for a color filter, and may be contained in an amount of 1 to 3% by weight. When the polymerization 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 can be improved.

The solvent is not particularly limited, and 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; Ketonic acid esters such as ethyl pyruvate; N, N-dimethylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformanilide, Hexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, Ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. These may be used alone or in combination of two or more.

From the viewpoint of compatibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; 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 are preferable.

In addition, the blue resin composition for a color filter may further contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots, anti-spotting, leveling characteristics, 3-amino-1,2-propanediol; A silane-based coupling agent having a vinyl group or (meth) acryloxy group; And the like.

On the other hand, the present invention provides a color filter manufactured using the above-mentioned blue resin composition. For example, the blue resin composition, the green resin composition, and the red resin composition may be formed on a substrate by a suitable method such as ink jet, spin coating, roll coating, . Thereafter, a UV ray, an electron beam, or an X ray is irradiated to form a pattern necessary for the color filter, and this is treated with an alkali developing solution to dissolve the unexposed portion of the coating layer and form a pattern necessary for the image color filter. This process is repeated according to the required number of R, G, and B colors to realize a color filter having a desired pattern.

The compound of the present invention is a triarylmethane compound in the form of a dimer having a displaceable anion and is capable of providing a blue resin composition for a color filter excellent in solubility and thermal stability and having a wide transmittance wavelength and excellent in solubility and heat resistance .

Fig. 1 shows the translucency spectra of the compounds of Example 1, Example 3 and Comparative Example.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the following examples.

Analysis of the compounds prepared in the following examples was carried out as follows: Nuclear magnetic resonance (NMR) spectral analysis was carried out using a Bruker Avance 300 spectrometer (Bruker), in which the chemical shift was in ppm Respectively. Molecular weight measurement using MALDI-TOF was performed using Bruker Autoflex Speed TOF / TOF (manufactured by Bruker).

In addition, the starting material of each example was purchased from Sigma-Aldrich as a known compound and used without purification.

Example 1: Preparation of the compound represented by the general formula (V)

(Step 1-1) Preparation of bis (4- (bis (2-hydroxyethyl) amino) phenyl) methanone

5 g (22.9 mmol) of 4,4'-difluorobenzophenone and 33.72 g (320.8 mmol) of diethanolamine were added, and the mixture was heated to 170 DEG C and stirred. Water and diethyl ether were added to separate the layers, and the aqueous layer was dried under reduced pressure and purified to obtain 6.22 g (16.03 mmol) of the title compound represented by Formula I above.

^{1 H NMR (300 MHz, CD} 3 OD): 7.63 (d, 4H), 6.81 (d, 4H), 3.76 (t, 8H), 3.64 (t, 8H)

¹³ C NMR (75 MHz, CD ₃ OD): 196.53, 152.83, 133.54, 126.72, 111.82, 60.18, 54.76

(Step 1-2) ((Carbonylbis (4,1-phenylene)) bis (azanetriyl)) tetrakis 2-yl) Of tetrakis (2-ethylhexanoate)  Produce

To 5 g (12.87 mmol) of the compound of the formula I prepared in the above Step 1-1, 12.56 g (77.22 mmol) of 2-ethylhexanoyl chloride and 2.93 g (28.96 mmol) of triethylamine were added to 300 ml of dichloromethane, And the mixture was heated to 60 DEG C and stirred. After the completion of the reaction, the mixture was cooled to room temperature, water was added, layer separation was carried out, and the resulting compound was concentrated under reduced pressure to obtain 6.2 g (6.95 mmol) of the title compound represented by the formula (II).

¹ H NMR (300 MHz, CDCl ₃ ): 7.74 (d, 4H), 6.82 (d, 4H), 4.30 m, 32H), 0.87 (t, 24H)

¹³ C NMR (75 MHz, CDCl ₃ ): 193.68, 176.43, 150.27, 132.56, 127.19, 110.87, 60.93, 49.62, 47.52, 31.80, 29.74, 25.49, 22.73, 14.06, 11.95

(Step 1-3) Polyethylene Of di (p-toluenesulfonate)  Produce

11.3 g (28.2 mmol) of polyethylene glycol (Mn = 400), 20.2 g (105.9 mmol) of p-toluenesulfonyl chloride and 12.8 g (127.1 mmol) of triethylamine were added to a 500 mL one- neck round bottom flask Stir for 24 hours. After completion of the reaction, methylene chloride and water were added to separate the layers, and the mixture was concentrated under reduced pressure, followed by purification to obtain the title compound (15.3 g) represented by the formula (III).

^{1 H NMR (300 MHz, CD} 3 OD): 7.80 (d, 4H), 7.45 (d, 4H), 4.14 (t, 4H), 3.66 (t, 4H), 3.31-3.63 (m, 24H), 2.44 (s, 6 H)

¹³ C NMR (75 MHz, CDCl ₃ ): 146.42, 134.43, 131.07, 129.03, 71.51, 71.45, 70.96, 69.69, 21.61

(Steps 1-4) O, O '- bis (2- (N- (1-naphthylaminoethyl))) polyethylene glycol

5 g (6.9 mmol) of the compound represented by the formula III prepared in the above step 1-3, 3.5 g (24.2 mmol) of 1-naphthylamine and 1.8 g (17.3 mmol) of sodium carbonate dissolved in a minimum amount of water were stirred. After completion of the reaction, water and dichloromethane were added thereto to separate the layers, and an organic layer was obtained. The organic layer was dried under reduced pressure and purified to obtain 1.35 g of the title compound represented by the formula (IV).

^{1 H NMR (300 MHz, CDCl} 3): 77.5-78.7 (m, 4H), 7.23-7.43 (m, 8H), 6.59 (d, 2H), 4.86 (s, 2H), 3.82 (t, 4H), 3.57 (m, 24 H), 3.42 (t, 4 H)

¹³ C NMR (75 MHz, CDCl ₃ ): 143.72, 134.41, 128.65, 126.67, 125.81, 124.74, 123.83, 120.34, 117.59, 104.57, 70.67, 70.38, 69.46, 43.74

(Step 1-5) Preparation of the compound represented by the general formula V

3.1 g (9.5 mmol) of 4,4-bis (diethylamino) benzophenone was added to 100 mL of toluene and stirred. Then, 6.9 g (45.1 mmol) of phosphorus oxychloride was added and stirred for 1 hour. Thereafter, 3.0 g (4.5 mmol) of the compound represented by the general formula (IV) prepared in 1-4 above was added, and the mixture was refluxed. After completion of the reaction, cooling at room temperature was carried out, water was added, and the mixture was stirred. After layer separation, concentration under reduced pressure was carried out and the obtained compound was purified to obtain 1.6 g of the title compound represented by the general formula (V). The weight average molecular weight of the obtained compound was 1,300 g / mol.

^{1 H NMR (300 MHz, (} CD 3) 2 SO): 8.49 (d, 2H), 8.39 (s, 2H), 6.77-7.40 (m, 26H), 3.43-3.73 (m, 58H), 1.17 (t , 24H)

¹³ C NMR (75 MHz, CDCl ₃ ): 175.17, 153.36, 143.03,139.28,136.28,128.28,127.99,126.98,126.13,125.76,123.68,123.59,112.02,104.52,70.45,69.12,45.32,43.28,12.65

MS (MALDI-TOF) 1520.7 [M < + >].

Example  2: BTFI  ≪ / RTI >

1.00 g (0.8 mmol) of the compound represented by the general formula (V) prepared in Example 1 was dissolved in methanol (50 mL) and 0.5 g (1.7 mmol) of bis (trifluoromethanesulfonylimide) Was added to replace the salt. After completion of the reaction, water was added thereto, the mixture was separated, and concentrated under reduced pressure to obtain 1.3 g of the title compound represented by the formula (V-BTFI). The weight average molecular weight of the obtained compound was 1,300 g / mol.

^{1 H NMR (300 MHz, (} CD 3) 2 SO): 8.22 (d, 2H), 8.39 (s, 2H), 6.77-7.40 (m, 26H), 3.43-3.73 (m, 58H), 1.17 (t , 24H)

¹³ C NMR (75 MHz, CDCl ₃ ): 175.17, 153.36, 143.03,139.28,136.28,128.28,127.99,126.98,126.13,125.76,123.68,123.59,112.02,104.52,70.45,69.12,45.32,43.28,12.65

MS (MALDI-TOF) 1520.7 [M < + >].

Example  3: Preparation of the compound represented by the formula (VI)

6.7 g (7.5 mmol) of the compound represented by the formula (II) prepared in Example 1 was added to 100 mL of toluene and stirred. Then 5.5 g (35.6 mmol) of phosphorus oxychloride was added and stirred for 1 hour. Thereafter, 2.4 g (3.6 mmol) of the compound represented by the formula IV prepared in Example 1 was added, and the mixture was refluxed. After completion of the reaction, cooling at room temperature was carried out, water was added, and the mixture was stirred. After layer separation, concentration under reduced pressure was carried out and the obtained compound was purified to obtain 1.8 g of the title compound represented by the formula (VI). The weight average molecular weight of the obtained compound was 2,400 g / mol.

^{1 H NMR (300 MHz, (} CD 3) 2 SO): 8.64 (s, 2H), 8.42 (d, 2H), 6.65-7.69 (m, 26H), 4.28 (t, 16H), 3.88 (t, 16H 4H), 3.51 (m, 4H), 3.43 (m, 24H), 2.18 (m, 8H), 1.09-1.43 (m, 64H), 0.78 48H)

¹³ C NMR (75 MHz, CDCl ₃ ): 176.15, 156.54, 152.70, 146.13, 138.30, 136.61, 129.54, 129.29, 127.40, 127.09, 126.84, 125.08, 124.12, 112.28, 106.98, 70.44, 69.29, 60.50, 49.73 , 47.10, 43.67, 31.57, 29.54, 25.27, 22.51, 13.90, 11.79

MS (MALDI-TOF) 2658.3 [M ^< ⁺ &^gt;] [

Example  4: BTFI  ≪ / RTI >

1.00 g (0.4 mmol) of the compound represented by the formula VI prepared in Example 3 was dissolved in methanol (50 mL), and lithium bistrifluoromethanesulfonimide (0.3 g, 0.9 mmol) was added thereto to replace the salt . After completion of the reaction, water was added thereto, the mixture was separated, and then concentrated under reduced pressure to obtain 1.1 g of the title compound represented by the formula VI-BTFI. The weight average molecular weight of the obtained compound was 2,400 g / mol.

^{1 H NMR (300 MHz, (} CD 3) 2 SO): 8.44 (s, 2H), 8.42 (d, 2H), 6.65-7.69 (m, 26H), 4.28 (t, 16H), 3.88 (t, 16H 4H), 3.51 (m, 4H), 3.43 (m, 24H), 2.18 (m, 8H), 1.09-1.43 (m, 64H), 0.78 48H)

¹³ C NMR (75 MHz, CDCl ₃ ): 176.15, 156.54, 152.70, 146.13, 138.30, 136.61, 129.54, 129.29, 127.40, 127.09, 126.84, 125.08, 124.12, 112.28, 106.98, 70.44, 69.29, 60.50, 49.73 , 47.10, 43.67, 31.57, 29.54, 25.27, 22.51, 13.90, 11.79

MS (MALDI-TOF) 2658.3 [M ^< ⁺ &^gt;] [

Comparative Example: Victoria Blue BO Compound

A compound represented by the following formula (XI), which is a widely used Victoria Blue BO compound, was used as a comparative example:

Experimental Example 1: Measurement of transmittance

In order to measure the transmittance of the compounds prepared in Examples 1 and 3 and the comparative examples, the respective compounds were analyzed using a UV-Vis spectrophotometer (UV3600 Plus, Shimadzu). The analysis was carried out by dissolving each compound in a chloroform solvent in an amount of 2% by weight and spin-coating the solution on a slide glass to form a film. The results are shown in FIG.

As shown in FIG. 1, it can be seen that the compounds of Formula 1 prepared in the Examples have a wider transmittance wavelength range than the Victoria Blue BO compounds of Comparative Examples. This can be attributed to the red and blue shifts of the transmission wavelengths of the compounds prepared in the Examples at the same time as those of the compounds of the Comparative Examples. Therefore, it is confirmed that the compounds represented by the above formula (1) can be used as a dye of a blue resin composition for a color filter.

Experimental Example 2: Evaluation of solubility

In order to measure the solubility (25 DEG C) in the solvent of the compounds prepared in Examples 1 to 4 and the compounds of the comparative examples, each compound was dissolved in propylene glycol monomethyl ether acetate (PGMEA) for 30 minutes, The solution was sieved using a syringe filter, the solvent was removed from the solution, and the weight of the remaining solute was measured. The measurement results are shown in Table 1 below.

Substituent
(R ₁ -R ₈ ) Anion
(X) Solubility
g / 100 g PGMEA Example 1 -C ₂ H ₅ Cl 3.0 Example 2 -C ₂ H ₅ BTFI 3.3 Example 3 _{- (CH 2) 2 -OC (} = O) -CH (C 2 H 5) (C 4 H 9) Cl 9.7 Example 4 _{- (CH 2) 2 -OC (} = O) -CH (C 2 H 5) (C 4 H 9) BTFI 10.2 Comparative Example -C ₂ H ₅ / H Cl 0.03

As shown in Table 1, the compounds of the formula (1) prepared in the examples show a solubility of 3 (g / 100 g PGMEA) or more, which is far superior to that of the Victoria Blue BO compound of the comparative example. Particularly, a compound having - (CH ₂ ) ₂ -OC (═O) -CH (C ₂ H ₅ ) (C ₄ H ₉ ) as a substituent of an amine has a high solubility of 9 (g / 100 g PGMEA) (Trifluoromethane) sulfonimide rather than chloride has a higher solubility than the compound in the form of a salt.

Accordingly, when the blue resin composition is prepared using the compound according to one embodiment of the present invention, the compound easily dissolves in the solvent of the composition, and thus it is easy to manufacture a color filter using an ink jet method or the like.

Experimental Example 3: Evaluation of thermal stability

In order to evaluate the thermal stability of the compounds prepared in Examples 1 to 4 and Comparative Examples, thermogravimetric analysis (TGA) was performed on each compound using a thermogravimetric analyzer Q500 (manufactured by TA Instruments) Respectively. Specifically, the analysis was carried out under the condition of increasing by 10 DEG C in 10 minutes, and as a result of the measurement, the residual weight (%) at 230 and the residual weight (%) at 250 were ascertained. The measurement results are shown in Table 2 below.

Residual weight at 230 ° C
(%) Residual weight at 250 ° C
(%) Example 1 96.90 94.75 Example 2 99.77 99.57 Example 3 97.47 96.64 Example 4 99.75 99.63 Comparative Example 82.92 69.10

As shown in Table 2, the compounds of the formula (1) prepared in the examples show remarkably high residual weight at 230 ° C and 250 ° C as compared with the Victoria Blue BO compound of the comparative example, indicating excellent thermal stability . Particularly, a compound having - (CH ₂ ) ₂ -OC (═O) -CH (C ₂ H ₅ ) (C ₄ H ₉ ) as a substituent of an amine exhibits a further improved thermal stability as compared with a compound having an ethyl group , Which is believed to be due to the hydrogen bonding between the oxygen of - (CH ₂ ) ₂ -OC (═O) -CH (C ₂ H ₅ ) (C ₄ H ₉ ) and the hydrogen of -NH 2.

Thus, the blue resin composition including the compound according to one embodiment of the present invention can realize a color filter exhibiting high brightness, high resolution, and high contrast ratio because the weight loss is very low at 230 ° C, which is the baking temperature required during the color filter manufacturing process .

Claims (10)

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

In Formula 1-1,
n is an integer of 1 to 100,
R ₁ to R ₈ are the same as each other and are - (CH ₂ ) ₂ -OC (═O) -CH (C ₂ H ₅ ) (C ₄ H ₉ ) or -C ₂ H ₅ ,
X is halogen, bis (trifluoromethane) sulfonimide, or trifluoromethanesulfonate.
delete delete delete delete The method according to claim 1,
Wherein X is chloride or bis (trifluoromethane) sulfonimide.
compound.
delete The method according to claim 1,
Wherein the compound represented by Formula 1-1 is selected from the group consisting of compounds represented by the following formulas:
compound:
[Formula V]

[Formula V-BTFI]

(VI)

[Formula VI-BTFI]

In the above Formulas V, V-BTFI, VI and VI-BTFI, n is an integer of 1 to 100.
A blue resin composition for a color filter, comprising the compound of any one of claims 1, 6, and 8.
A color filter produced by using the blue resin composition for a color filter according to claim 9.

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