KR20180058329A - A novel perylene compound and use thereof - Google Patents

Abstract

The present invention relates to a novel dye compound and uses thereof. More particularly, the present invention provides a novel fluorescence-inhibited perylene dye compound which can be used as a color filter of a display element, a dye composition containing the same, and various uses such as a color filter. The dye composition of the present invention comprises: a perylene compound; a solvent; and a binder resin and a polymerizable compound.

Description

A novel perylene compound and use thereof,

The present invention relates to a novel compound and its use, and more particularly to a novel perylene compound which can be used for a color filter or the like and its use.

The color filters are formed on the transparent substrate such as glass and have pixel portions of three colors of red, green, and blue. The color filters used in the image display apparatus such as LCD and the solid-state image pickup device are typically red (R), green G), and blue (B), and has a function of coloring the passing light or separating the light into three primary colors.

The development of technology for the large-screen and high-definition liquid crystal display has been progressing, and its use has been greatly expanded from a display for a laptop computer to a monitor for a desktop computer and a television monitor. In such a situation, a color filter used for a liquid crystal display or the like is required to have a high contrast ratio.

Korean Patent Laid-Open Publication No. 2014-0147037 discloses a perylenebismide-based compound, and Korean Laid-Open Patent Application No. 2015-0115550 discloses a perylene-based compound and a red ink containing the same. In addition, Choi et al . Disclose dyes of several perylene sites available as LCD color filters (Choi et al ., Dyes and Pigments, 90: 82-88, 2011).

However, conventionally developed perylene dyes for color filters including the above-mentioned prior art have disadvantages in that the minimum brightness value is increased due to strong fluorescence and the contrast ratio is lowered. The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a sample cloud pigment compound having improved optical characteristics such as color uniformity, contrast ratio and brightness, and a color filter thereof . However, these problems are exemplary and do not limit the scope of the present invention.

 According to one aspect of the present invention there is provided a perylene-based compound having the structure:

In the above structural formulas, R ₁ to R ₄ are each independently methyl, ethyl, methoxy, or ethoxy.

The perylene-based compound may more specifically have the following structural formula:

.

.

The perylene-based compound may be a compound having the following IUPAC designation:

2,9-bis (2-methoxy-6-methylphenyl) -5,12-bis (4-methoxyphenoxy) anthra [2,1,9-dis: 6,5,10-d] 1,3,8,10 (2H, 5H, 5b1H, 9H) -tetraone.

According to another aspect of the present invention, there is provided a dye composition comprising the perylene-based compound.

According to another aspect of the present invention, there is provided a color filter comprising the perylene-based compound.

According to one embodiment of the present invention as described above, it is possible to realize a dye capable of improving optical characteristics such as contrast ratio and brightness in a solid scratch-off element, a liquid crystal display or an organic EL display. Of course, the scope of the present invention is not limited by these effects.

1 shows ¹ H NMR data of a perylene-based compound PI-4ME prepared according to an embodiment of the present invention.
2 shows ¹³ C NMR data of perylene-based compound PI-4ME prepared according to an embodiment of the present invention.
3 shows ¹ H NMR data of perylene-based compound PM-4ME prepared according to an embodiment of the present invention.
4 shows ¹³ C NMR data of perylene-based compound PM-4ME prepared according to an embodiment of the present invention.
FIG. 5 is a fluorescence spectrum obtained by measuring the fluorescence properties of four compounds (PI-4ME, PM-4ME, PI-4EP and PM-4EP) prepared according to an embodiment of the present invention, wherein A is chloroform as a solvent And B is a color filter prepared by spin-coating a resin composition prepared by mixing the above-mentioned four kinds of dyes with an acrylic binder in a solvent and measuring the concentration of each dye by adjusting the concentration of each dye to 10 ^-5 mol / The fluorescence spectrum is a fluorescence spectrum.

 According to one aspect of the present invention there is provided a perylene-based compound having the formula:

In the above structural formulas, R ₁ to R ₄ are each independently methyl, ethyl, methoxy, or ethoxy.

The perylene-based compound may more specifically have the following structural formula:

The perylene-based compound may be a compound having the following IUPAC designation:

2,9-bis (2-methoxy-6-methylphenyl) -5,12-bis (4-methoxyphenoxy) anthra [2,1,9-dis: 6,5,10-d] 1,3,8,10 (2H, 5H, 5b1H, 9H) -tetraone.

The above compound can be prepared through the following reaction formula.

(Scheme)

The present inventors have found that PI-4ME and PM-4ME among the compounds prepared according to the above reaction scheme exhibit highly suppressed fluorescence unlike PI-4EP and PM-4EP (FIG. 5) Thereby completing the invention. Therefore, the compound according to one embodiment of the present invention can be used not only as a general red pigment but also as a color filter by suppressing fluorescence while securing high solubility, thereby minimizing a decrease in contrast ratio as well as raising a minimum brightness value It can be very useful for manufacturing a high-quality display device.

According to another aspect of the present invention, there is provided a dye composition comprising the perylene-based compound.

The dye composition may be dissolved in a suitable solvent so that the perylene-based compound is well dispersed. Examples of the solvent include methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, Dipropylene glycol monomethyl ether, and the like, but is not limited thereto.

The content of the solvent is preferably 45 to 95% by weight based on the total weight of the composition, but is not limited thereto.

The dye composition may further comprise, in addition to the dye and the solvent, a binder resin and a polymerizable compound.

The dye composition may further contain one or more compounds selected from the group consisting of photoinitiators, curing accelerators, thermal polymerization inhibitors, dispersants, antioxidants, ultraviolet absorbers, leveling agents, photosensitizers, plasticizers, adhesion promoters, fillers, Additives may additionally be included.

In the dye composition, those commonly used in the art such as an alkali-soluble binder resin may be used as the binder resin. Concretely, an acrylic binder resin containing a carboxyl group as an alkali-soluble resin can be used, and a resin having a weight average molecular weight of 3,000 or more and 150,000 or less can be used.

The content of the binder resin may be 1 to 20% by weight based on the total weight of the dye composition, but is not limited thereto.

In the dye composition, the polymerizable compound may be an acrylate-based compound. Specifically, the polymerizable compound may be at least one compound selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) May be used, but is not limited thereto.

The content of the polymerizable compound is preferably 1 to 30% by weight based on the total weight of the dye composition, but is not limited thereto.

In the dye composition, the photoinitiator may be 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'- methoxystyryl) (2-hydroxyphenoxy) -phenyl (2-hydroxyphenyl) -triazine, 2,4-trichloromethyl- (phenylonyl) 6-triazine, 1-hydroxycyclohexyl phenyl ketone, 4- Propyl ketone, benzophenone, 2,4,6-trimethylaminobenzophenone and the like can be used, but the present invention is not limited thereto.

The content of the photoinitiator is preferably 0.1 wt% or more and 5 wt% or less based on the total weight of the composition, but is not limited thereto.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercaptan-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris And trimethylol ethane tris (3-mercaptopropionate). However, the present invention is not limited thereto and may include those generally known in the technical field of the present invention.

Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine Aluminum salts, and phenothiazines. However, the present invention is not limited thereto, and may include those generally known in the art.

Any compound that can be included in conventional curable resin compositions can be used as the surfactant, photosensitizer, plasticizer, adhesion promoter, filler, dispersant, antioxidant, ultraviolet absorber and leveling agent.

According to one aspect of the invention, a filter segment comprising the dye composition is provided. The filter segment may be, but is not limited to, a purple filter segment.

According to another aspect of the present invention, there is provided a color filter including the filter segment. The color filter may further include a substrate, a black mattress, and a color pattern, and the color pattern may be a red pattern.

Hereinafter, the present invention will be described in more detail by way of examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, Is provided to fully inform the user.

Example 1: Preparation of perylene-based compound

Unless specifically mentioned in the examples of the present invention, the compounds and solvents used were all Sigma-Aldrich products.

1-1: Preparation of 1,7-dibromopheryline-3,4,9,10-tetracarboxydimide

32.00 g (81.40 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride, 0.78 g (3.04 mmol) of iodine and sulfuric acid (98% ) Were mixed and stirred at room temperature for 2 hours. After the temperature of the mixture was raised to 80 ° C, bromine (8.33 ml, 162.80 mmol) was added dropwise for 1 hour. The resulting mixture was reacted for 16 hours, cooled to room temperature, and the residual bromine gas was replaced with nitrogen gas. The mixture was then slowly poured into 3 L of ice water to form a crude precipitate, which was filtered through suction to give the crude precipitate which was washed several times with distilled water. The crude product thus obtained was dried under reduced pressure at 80 ° C and used in the next step without further purification ((1)).

1-2: N, N'-bis (R ₅ ) -1,7-dibromopheryline-3,4,9,10-tetracarboxydiimide

8.00 g of 1,7-dibromoperylene diisocyanate (1,7-dibromoperylene-3,4,9,10-tetracarboxydiimide) prepared in Example 1-2 (14.55 mmol), 45.00 mmol of 2,6-diisopropylaniline or 2-methoxy-6-methylaniline with R ₅ -NH ₂ , And 100 ml of N-methyl-2-pyrrolidone (NMP) were mixed and heated at 120 占 폚 under a nitrogen atmosphere for 96 hours. Water was then added to the mixture and the resulting precipitate was obtained by suction filtration. The obtained crude product was washed with water and dried under reduced pressure. The crude product was purified by column chromatography with silica gel loaded with methylene chloride (CH ₂ Cl ₂ ) as eluent, resulting in the collection of three bands. The first band contained a small amount of tribrominated diimide and the second band contained dibrominated diimide, a precursor of the compound according to one embodiment of the present invention (Rf = 0.55) , And the third band included monobrominated diimide. That is, the second band from the N, N'- bis (R ₅₎ -1,7- di-bromo mope Lilin -3,4,9,10- tetrahydro carboxy diimide (N, N'-bis (R 5) -1,7-dibromoperylene-3,4,9,10-tetracrylic diimide) was obtained ((2) in the above reaction scheme).

1-3: N, N'-bis (R ₅ ) -1,7-bis (p-methoxyphenoxy) -perylene-3,4,9,10-tetracarboxydimide

0.58 mmol of N, N'-bis (R ₅ ) -1,7-dibromopherylin-3,4,9,10-tetracarboxydimide prepared in Example 1-2 was dissolved in anhydrous potassium carbonate 0.35 g (2.54 mmol) of anhydrous potassium carbonate, 0.20 g (1.61 mmol) of 4-methoxyphenol and 60 ml of NMP. The mixture was stirred for 1.5 hours while heating to 40 < 0 > C under a nitrogen atmosphere. The mixture was then cooled to ambient temperature and added to 400 mL of 5% aqueous hydrochloric acid solution. The resulting precipitate was collected by suction filtration, washed with water and vacuum dried at 80 < 0 > C. Using methylene chloride as eluent The crude product was silica gel jeongjae in the filled column chromatography, and the results as a red solid N, N'- bis (R ₅₎ -1,7- bis (p- methoxyphenoxy ) - Fe Lilin -3,4,9,10- tetrahydro carboxy diimide (N, N'-bis (R 5) -1,7-bis (p-methoxyphenoxy) -perylene-3,4,9,10- tetracarboxydiimide) ((3) in the above reaction scheme). The yield was 82.1% for PI-4ME and 78.4% for PM-4ME.

2,6-diisopropylphenyl) -5,12-bis (4-methoxyphenoxy) anthra [2,1,9-def: 6,5,10-d (2-methoxy-6-methylphenyl) pyrazole of formula (2) was named PI-4ME for convenience. -5,12-bis (4-methoxyphenoxy) anthra [2,1,9-dis: 6,5,10-d] [e '] diisoquinoline-1,3,8,10 (2H, 5H, 5b1H, 9H) -tetraone was named PM-4ME. The ¹ H NMR and ¹³ C NMR data of each of the two compounds PI-4ME and PM-4ME are shown in FIGS. 1-4. As shown in Figs. 1 to 4, it was confirmed that compounds corresponding to the respective formulas were produced.

In addition, the present inventors prepared 2,9-bis (4-methoxyphenol) of formula (4) in the same manner as above except that 4-ethylphenol was used instead of 4-methoxyphenol used in (3) (2,6-diisopropylphenyl) -5,12-bis (4-ethylphenoxy) anthra [2,1,9-dis: 6,5,10-d] [e '] diisoquinoline-1,3,8,10 (2H, 5H, 5b1H, 9H) -tetraone and 5,12-bis (4-ethylphenoxy) -2,9- bis (2-methoxy- 6- methylphenyl) anthra [ Dihydroquinoline-1,3,8,10 (2H, 5H, 5b1H, 9H) -tetraone was named PI-4EP and PM-4EP, respectively.

Example 2: Preparation of color filter

The present inventors blended 16 mg of each of the dye compounds obtained in Example 1 with 0.8 g of an acrylic binder, LC20160 (Samsung Cheil Industries, Inc., Korea), 0.1 g of propylene glycol methyl ether acetate (PGMEA) Coated on a transparent glass substrate with a MIDAS System SPIN-1200D spin coater at 100 rpm for 10 seconds and then at 500 rpm for 20 seconds, followed by drying at 80 ° C for 20 minutes and then pre-baking at 150 ° C for 10 minutes. baking and post-baking at 200 ° C for 1 hour to produce a film, which was used as a red filter.

Experimental Example 1: Solubility Analysis of Dye Solvent

In order to use dyes for various purposes, especially for color filters such as LCDs, they must be soluble in organic solvents and have good dispersibility in polymeric materials for filming. However, in general, the perylene-based dyes have strong tinctorial strength and thermal stability due to their high planarity, while solubility in commercial organic solvents such as propylene glycol methyl ether acetate (PGMEA), which is a commercially available organic solvent commonly used in LCD manufacturing processes Is not good. Thus, the present inventors measured the solubility of the dye compound prepared in Example 1 in various organic solvents.

Specifically, the solubilities of the four dye compounds prepared in Example 1 above were measured for methylene chloride (CH2Cl2), chloroform (CHCl3) and PGMEA.

As a result, as shown in Table 1, the introduced large substituent showed sufficient solubility to be used as an LCD color filter.

Solubility in various organic solvents dyes PI-4EP PI-4ME PM-4EP PM-4ME CH2Cl2 5.8 5.9 5.2 5.1 CHCl3 6.0 6.0 5.7 5.8 PGMEA 5.0 5.1 4.7 4.8

Experimental Example 2: Fluorescence characterization of a filter containing a dye and a dye

After dissolving the dye compounds PI-4ME, PM-4ME, PI-EP and PM-4EP prepared in Example 1 in a concentration of 10 ^-5 mmol / L using chloroform as a solvent, Their absorption spectra were measured using a UV / Vis spectrophotometer (Perkin Elmer Lamda 25, USA). As a result, as shown in Fig. 5 and Table 2, it was confirmed that the four dye compounds were red dyes having almost similar absorption spectra showing maximum absorbance at 546 to 552 nm. Then, the present inventors dissolved the dye compound in chloroform at a concentration of 10-8 mmol / L and measured the maximum absorption wavelength, the extinction coefficient per mole, the maximum emission wavelength, and the maximum emission intensity using a fluorescence spectrophotometer (Perkin Elmer LS 55, USA) , Fluorescence intensities such as the integrated value of the fluorescence intensity in the visible light region, the maximum absorption-emission wavelength difference (? SS), and the quantum yield were analyzed. At this time, except for the quantum yield of the fluorescence properties, light of the wavelength recorded at the maximum absorption wavelength measured in the absorption spectrum analysis for the compound was used. The quantum yield was measured using light having a wavelength of 480 nm.

Various optical properties of dye compounds dyes PI-4EP PI-4ME PM-4EP PM-4ME Maximum absorption wavelength (nm) 546 550 548 552 The absorption coefficient (L / mol cm) 62,049 56,653 56,508 59,998 Maximum emission wavelength (nm) 581 586 580 582 Maximum emission intensity 241.82 7.07 226.75 10.20 The integral value of the fluorescence intensity in the visible light region 29,305.99 856.53 27,623.99 1,257.39 Maximum absorption-emission wavelength difference (? SS) 35 36 32 30 The quantum yield (10-5 mol / L in chloroform, excitation at 480 nm) 0.966 0.054 0.948 0.079

As a result of the analysis, as shown in FIG. 6A, PI-4ME and PM-4ME according to an embodiment of the present invention showed fluorescence characteristics in which almost no fluorescence was observed. Whereas PI-4EP and PM-4EP emitted very high fluorescence at 585 nm. This means that the methoxy group introduced at the terminal has no effect on the fluorescence quenching, while the methoxy group introduced at the bay position dramatically reduces fluorescence. That is, it suggests that the bay-substitution has a strong influence on the [pi] -bond system and electrochemical characteristics of the dyes. Interestingly, in the case of PI-4EP, a compound corresponding to PI-4ME, a methoxy group is present at the 4-carbon position of the phenoxy group in the substituted benzyl substituent instead of the bromine group of dibromotetracarboxydimide, Although there is a difference, there is a completely different fluorescence characteristic.

Thus, the present inventors performed the same analysis as above on the color filter film prepared in Example 2 to confirm that the characteristics of the dye compound were maintained even in the film formed by mixing with the resin composition.

As a result, as shown in FIG. 6B, even though the maximum emission wavelength was slightly different from the dye dissolved in chloroform, the PI-4ME and PM-4ME compounds according to one embodiment of the present invention exhibited highly suppressed fluorescence properties , Control compounds PI-4EP and PM-4EP emitted strong fluorescence near 620 nm.

As demonstrated above, since the dye compound according to one embodiment of the present invention exhibits highly suppressed fluorescence, it is possible to manufacture a dye-type color filter capable of minimizing the reduction of the contrast ratio, It can be very useful for the material industry.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. I will understand. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (14)

According to one aspect of the present invention, there is provided a perylene-based compound having the following structural formula:

In the above structural formulas, R ₁ to R ₄ are each independently methyl, ethyl, methoxy, or ethoxy. The method according to claim 1,
A perylene compound having the following structural formula:

. A dye composition comprising a perylene-based compound. The method of claim 3,
≪ / RTI > further comprising a solvent. 5. The method of claim 4,
Wherein the solvent is at least one compound selected from methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether, and the like. 5. The method of claim 4,
A binder resin, and a polymerizable compound. 8. The method of claim 7,
Wherein the binder resin is an alkali-soluble binder resin. The method according to claim 6,
Wherein the polymerizable compound is an acrylate compound. 9. The method of claim 8,
The acrylate compound is at least one compound selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Dye composition. The method according to claim 6,
Wherein the composition further comprises one or more additives selected from the group consisting of a photoinitiator, a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, an ultraviolet absorber, a leveling agent, a photosensitizer, a plasticizer, an adhesion promoter, a filler, Dye composition. 11. The method of claim 10,
The photoinitiator may be 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'- methoxystyryl) 4-trichloromethyl- (phenylonyl) 6-triazine, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2- hydroxy) propyl ketone, benzophenone, 2 , 4,6-trimethylaminobenzophenone, and the like. 11. The method of claim 10,
The curing accelerator may be selected from the group consisting of 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercaptan-1,3,4-thiadiazole, (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate). ≪ / RTI > A filter segment comprising the dye composition of claim 3. 14. A color filter comprising the filter segment of claim 13.

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