KR101961093B1 - Perylene bisimide based compounds and dyes comprising the same - Google Patents
Perylene bisimide based compounds and dyes comprising the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
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Abstract
The present invention provides a perylene bisimide compound represented by the following general formula (1), and provides a dye exhibiting not only excellent fluorescence efficiency but also excellent chemical, thermal and photochemical stability.
[Chemical Formula 1]
R 1 to R 6 in Formula 1 are the same as those defined in the specification.
Description
The present invention relates to a compound containing a perylene bimide-based structure and a dye containing the same.
As a flat panel display device, a liquid crystal display device has been widely used. BACKGROUND ART [0002] Liquid crystal display devices require a backlight as a separate light source and have technical limitations in terms of brightness and contrast ratio. Accordingly, there is an increasing interest in an organic light emitting device (OLED) that is self-luminous and does not require a separate light source and is relatively superior in brightness and contrast ratio to a liquid crystal display device.
There are RGB and WOLED methods to implement color in OLED.
The RGB method is advantageous in that the luminance is not reduced because the color filter is not necessary and the OLED light emitting material is transmitted as it is. However, since a fine metal mask (FMM) is used for depositing organic materials, There is a problem that the process yield is lowered and it is difficult to apply to a large-sized TV. Therefore, WOLED is proposed as an alternative to FMM.
In the WOLED method, light of white (W) emitted from the light emitting layer is filtered while passing through the color filter layer, thereby emitting light of red (R), green (G) or blue (B) And displays an image. The WOLED method is advantageous for mass production because it does not need to use FMM because it becomes larger and easier to process. However, since the color filter is incorporated, the luminance and color gamut are inferior to those of RGB type OLED.
In order to solve such problems of low luminance and color reproducibility, a method of introducing a color conversion layer (CCL) using a fluorescent dye has attracted attention.
The fluorescent material is excited by the blue light emitted from the WOLED to emit green and red light, thereby improving the luminous efficiency of the green and red pixels, thereby improving the brightness and improving the color reproduction rate. Such a fluorescent substance must have high heat resistance and light resistance, and should have high solubility in order to facilitate a color conversion layer production process.
A problem to be solved by the present invention is to provide a perylene bisimide compound improved in solubility and fluorescence efficiency as well as chemical, thermal and photochemical stability.
Another object of the present invention is to provide a dye comprising the perylene bisimide compound.
In order to solve the problems of the present invention, there is provided a perylene bisimide compound represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
R1 and R2 are each independently a substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; A substituted or unsubstituted straight or branched chain alkyl group,
Each of R3, R4, R5 and R6 independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted thiophenoxy group And R3, R4, R5 and R6 are not all the same,
[Structural formula 1]
In the above formula 1
X1 and X5 are hydrogen atoms,
X2, X3 and X4 are each independently a hydrogen atom or a halogen atom, at least one of X2, X3 and X4 is a halogen atom,
Y is an oxygen (O) atom or a sulfur (S) atom.
According to one embodiment, the perylene bisimide compound represented by Formula 1 may be represented by Formula 2 below.
(2)
In Formula 2,
R1 and R2 are the same as defined in formula (1)
R11, R12, R13 and R14 each independently represents a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, At least one of R11, R12, R13 and R14 is different from the others in the kind of the substituent or the position of the substituent, and R11, R12, R13 and R14 are not all the same,
The substituent of at least one of R11, R12, R13 and R14 may be substituted at the para or meta position,
Y1, Y2, Y3 and Y4 are each independently an oxygen (O) atom or a sulfur (S)
a, b, c, and d are each independently an integer of 1 to 5;
According to one embodiment, R 1 or R 2 may be a substituent represented by the following formula (2).
[Structural formula 2]
In the above formula 2,
R 21 to R 25 are each independently a substituent selected from hydrogen and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
According to one embodiment, the perylene bisimide compound represented by Formula 1 may be represented by any one of the following Formulas 3-1 to 3-12.
[Formula 3-1]
[Formula 3-2]
[Formula 3-3]
[Chemical Formula 3-4]
[Formula 3-5]
[Chemical Formula 3-6]
[Chemical Formula 3-7]
[Chemical Formula 3-8]
[Chemical Formula 3-9]
[Chemical Formula 3-10]
[Formula 3-11]
(3-12)
The present invention also relates to
Dissolving the compound of formula (IV) and potassium carbonate in a reaction solvent and then raising the temperature to the reaction temperature;
Adding at least two kinds of phenol compound solutions dissolved in the same reaction solvent as the reaction solvent and potassium carbonate at the reaction temperature; And
Cooling the reaction solution to room temperature, discharging it to distilled water, and filtering it under reduced pressure. The present invention also provides a method for producing the perylene bisimide compound.
[Chemical Formula 4]
According to one embodiment, the reaction temperature may be 100-150 ° C.
According to one embodiment, the two or more phenol-based compounds each contain different substituents or have different substituent positions. In each phenol-based compound, at least one substituent in the substituent group is para or meta meta) position.
In order to solve the other problems of the present invention, there is provided a dye comprising the perylene bisimide compound.
The perylene bisimide compound according to the present invention can exhibit excellent chemical, thermal and photochemical stability, and can exhibit excellent fluorescence efficiency under a high concentration and can be easily dissolved in a solvent, thereby improving the efficiency of the process.
Hereinafter, the present invention will be described in more detail.
The application of red phosphors to white LEDs has mainly consisted of inorganic oxide, sulfide and nitride systems. However, the inorganic oxide system exhibits low excitation characteristics in the blue region, and the sulfide system has a problem that the chemical stability thereof is very low. Further, the nitride phosphors are capable of emitting light in a higher wavelength band (yellow or red) than the oxide phosphors, and have high stability. However, the nitride phosphors are disadvantageous in terms of brightness and have a problem in that they are subject to many limitations in manufacturing such as reacting metal nitride at high temperature and high pressure .
In addition, the fluorescent material is excited by the blue light emitted from the WOLED to emit green and red light, thereby improving the luminous efficiency of the green and red pixels, thereby improving not only the luminance but also the color reproduction rate. These fluorescent materials must not only have heat resistance and light resistance, but also have high solubility in order to facilitate the color conversion layer production process. Generally, the color conversion layer is formed by using a color resist in the form of an ink containing a fluorescent dye, and propylene glycol monomethyl ether acetate (PGMEA) is generally used as a solvent for such a color resist. However, the known fluorescent dyes have little or no solubility in PGMEA and thus are difficult to apply.
In order to solve these problems, the present inventors have studied the possibility of improving the solubility according to the structure of the fluorescent dyes, and as a result, invented a perylene bisimide compound having a specific substituent.
The present invention provides a perylene bisimide compound which not only exhibits excellent properties in heat resistance and light resistance, but also has improved solubility and fluorescence efficiency.
The present invention provides a perylene bisimide compound represented by the following general formula (1) for solving the conventional problems.
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted straight-chain or branched-chain alkyl group,
R3, R4, R5 and R6 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted thiophenoxy group, R 3, R 4, R 5 and R 6 are not all the same,
[Structural formula 1]
In the above formula 1
X1 and X5 are hydrogen atoms,
X2, X3 and X4 are each independently a hydrogen atom or a halogen atom, at least one of X2, X3 and X4 is a halogen atom,
Y is an oxygen atom or a sulfur atom.
According to one embodiment, the perylene bisimide compound represented by Formula 1 may be one in which at least one of halogen-substituted aryloxy or thiophenoxy is substituted.
According to the present invention, perylene bisimide compounds into which a halogen-substituted aryloxy group or thiophenoxy group is introduced can increase fluorescence,
By inducing structural distortions by introducing substituents in asymmetric form, solubility in solvents can be increased. In addition, it can exhibit excellent chemical, thermal and optical stability, which is very advantageous for the application of the process.
According to one embodiment, the perylene bisimide compound represented by Formula 1 may be represented by Formula 2 below.
(2)
In Formula 2,
R1 and R2 are the same as defined in formula (1)
R11, R12, R13 and R14 each independently represents a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, And at least one of R11, R12, R13 and R14 is a substituent selected from the group consisting of a substituent and a substituent,
Y1, Y2, Y3 and Y4 are each independently an oxygen (O) atom or a sulfur (S)
a, b, c, and d are each independently an integer of 1 to 5;
According to one embodiment, at least one substituent of R11, R12, R13 and R14 may be substituted at para or meta position.
According to one embodiment, in Formula 1, R 1 or R 2 may be a substituent represented by Formula 2 below.
[Structural formula 2]
In the above formula 2,
R21 to R25 each independently represent a substituent selected from a hydrogen atom and a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms.
As used herein, the term "substituted or unsubstituted" means a group selected from the group consisting of a halogen group, a nitrile group, a nitro group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a thiol group, An alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, a heterocyclic group and an acetylene group, which is selected from the group consisting of an alkyl group, an aryl group, an aryl group, an aryl group, Substituted with one or more substituents, or have no substituent.
In the present specification, the "halogen group" means -F, -Cl, -Br or -I.
According to one embodiment, the compound of Formula 1 may be a compound represented by any one of the following Formulas 3-1 to 3-12, but is not limited thereto.
[Formula 3-1]
[Formula 3-2]
[Formula 3-3]
[Chemical Formula 3-4]
[Formula 3-5]
[Chemical Formula 3-6]
[Chemical Formula 3-7]
[Chemical Formula 3-8]
[Chemical Formula 3-9]
[Chemical Formula 3-10]
[Formula 3-11]
(3-12)
The perylene bisimide compound according to the present invention is a perylene bisimide compound,
May be prepared by reacting a compound of the following formula (4) with a compound containing a substituent to be substituted,
Dissolving the compound of formula (IV) and potassium carbonate in a reaction solvent and then raising the temperature to the reaction temperature;
Adding at least two kinds of phenol compound solutions dissolved in the same reaction solvent as the reaction solvent and potassium carbonate at the reaction temperature; And
Cooling the reaction solution to room temperature, discharging it to distilled water, and filtering it under reduced pressure.
[Chemical Formula 4]
Specifically,
Heating the reaction solvent containing the compound of Formula 4 and potassium carbonate to a reaction temperature of 100 to 150 ° C;
Adding the first phenolic compound solution dissolved in the reaction solvent at the reaction temperature and holding the solution for a predetermined time;
Adding a second phenolic compound solution at the same temperature as the reaction temperature;
Adding potassium carbonate to the reaction solution; And
Cooling the reaction solution to room temperature, discharging it to distilled water, and filtering it under reduced pressure.
According to one embodiment, in addition to the first phenol compound and the second phenol compound, a third phenol compound or a fourth phenol compound may be further added, and the two or more phenol compounds may have different substituents , Or the positions of the substituents are different. It is preferable that at least one substituent in the substituent group in each phenol compound is substituted at the para or meta position.
According to one embodiment, the total molar amount of the two or more phenolic compounds may be added in excess with respect to the molar content of the compound of formula 4, for example, in a molar ratio of 4.2: 1 to 6: 1 , More preferably 4.5: 1 to 5.5: 1, to further improve the reactivity.
The present invention also provides a dye comprising the perylene bisimide compound.
According to one embodiment, the dye may be a red dye and may be excellent in stability and fluorescence efficiency.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.
PREPARATION EXAMPLE 1 Synthesis of Intermediate Compound (INT)
1,6,7,12-Tetrachloroperylene tetracarboxylic acid dianhydride (0.11 mol) and 2,6-diisopropylaniline (0.44 mol) were added to 1 L of propionic acid, and the temperature was raised to maintain the reaction at 140 ° C. for 5 hours. The reaction solution was cooled to room temperature, and the precipitate was filtered under reduced pressure and washed with methanol. The filtrate was dispersed in water, kept for 30 minutes, then filtered under reduced pressure, dispersed again in methanol, held for 30 minutes, and then filtered under reduced pressure. After drying, the intermediate compound (INT) was obtained in a yield of 80.5%. The synthesis reaction of the intermediate compound (INT) is shown in the following reaction formula (1).
MS (Mass Spectrometric) was measured for the intermediate compound formed using a MALDI-TOF measuring apparatus. MS: 848.16
[Reaction Scheme 1]
Example 1 Preparation of Compound of Formula 3-1
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4-fluorophenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 占 폚 for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain the compound of Formula 3-1 in a yield of 40.4%. The above reaction is shown in Reaction Scheme 2 below.
MS: 1198.29
[Reaction Scheme 2]
Example 2 Preparation of Compound of Formula 3-2
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4- (tert-butyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain a compound of Formula 3-2 in a yield of 37.0%. The above reaction is shown in Reaction Scheme 3 below.
MS: 1236.37
[Reaction Scheme 3]
Example 3: Preparation of the compound of the formula 3-3
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 2,4-di-tert-butylphenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain the compound of Formula 3-3 in a yield of 62.4%. The above reaction is shown in Reaction Scheme 4 below.
MS: 1292.43
[Reaction Scheme 4]
Example 4: Preparation of the compound of the formula 3-4
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4-chlorophenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-bromophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain a compound of Formula 3-4 in a yield of 60.3 % . The above reaction is shown in Reaction Scheme 5 below.
MS: 1348.11
[Reaction Scheme 5]
Example 5: Preparation of the compound of the formula 3-5
Potassium carbonate (0.08 mol) was added to the solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4- (tert-butyl) phenol (0.08 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.12 mol) and potassium carbonate (0.12 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain the compound of Formula 3-5 in a yield of 28.0%. The reaction is shown in Scheme 6 below.
MS: 1258.47
[Reaction Scheme 6]
Example 6 Preparation of Compound of Formula 3-6
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. And a solution prepared by dissolving 3-chlorophenol (0.04 mol) in N-methylpyrrolidone (88.7 g) at 120 ° C for 2 hours was added to the reaction solution. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain the compound of Formula 3-6 in a yield of 80.5%. The above reaction is shown in Reaction Scheme 7 below.
MS: 1216.26
[Reaction Scheme 7]
Example 7 Preparation of Compound of Formula 3-7
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. (0.04 mol) of N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain a compound of Formula 3-7 in a yield of 68.7%. The above reaction is shown in Reaction Scheme 8 below.
MS: 1280.35
[Reaction Scheme 8]
Example 8 Preparation of a compound of the formula 3-8
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution prepared by dissolving 4-bromophenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain a compound of formula 3-8 in a yield of 70.6%. The above reaction is shown in Reaction Scheme 9 below.
MS: 1258.21
[Reaction Scheme 9]
Example 9 Preparation of the compound of the formula 3-9
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4- (tert-butyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-bromophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), followed by silica filtration to remove impurities and recrystallization from MeOH yielded the compound of formula 3-9 in 56.5% yield. The above reaction is shown in Reaction Scheme 10 below.
[Reaction Scheme 10]
Example 10 Preparation of Compound of Formula 3-10
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4- (tert-butyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorobenzene thiol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), followed by silica filtration to remove impurities and recrystallization from MeOH yielded the compound of formula 3-10 in a yield of 56.5%. The above reaction is shown in the following reaction formula (11).
MS: 1370.21
[Reaction Scheme 11]
Example 11 Preparation of Compound of Formula 3-11
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 4-chlorobenzenethiol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, potassium carbonate (0.04 mol) was added, and a solution obtained by dissolving 4- (tert-butyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) Lt; / RTI > After maintaining the reaction at 120 DEG C for 1 hour, 4-chlorophenol (0.12 mol) and potassium carbonate (0.12 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain the compound of Formula 3-11 in 66.6% yield. The above reaction is shown in Reaction Scheme 12 below.
MS: 1252.34
[Reaction Scheme 12]
Example 12: Preparation of a compound of the formula 3-12
Potassium carbonate (0.04 mol) was added to the dissolved solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Preparation Example 1, and the temperature was raised to 120 ° C. A solution of 3- (trifluoromethyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain a compound of Formula 3-12 in a yield of 40.5%. The above reaction is shown in the following reaction formula (13).
MS: 1248.29
[Reaction Scheme 13]
≪ Comparative Example 1 &
≪ Comparative Example 2 &
≪ Comparative Example 3 &
≪ Production of Resin Composition >
Resin compositions containing the dye compounds of Examples 1 to 12 and Comparative Examples 1 to 3 were prepared in the following manner.
, 1.4 g of a copolymer (Mw = 20,000) of benzyl methacrylate / methacrylic acid (weight ratio 60:40) as binder resin, 5.0 g of dipentaerythritol hexaacrylate as an acrylic monomer, 0.1 g of a dye compound , 1.0 g of Irgacure OXE-02 manufactured by BASF as a photopolymerization initiator, and 40.7 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed and stirred for 2 hours to prepare a resin composition.
Experimental Example 1: Evaluation of solubility
For solubility measurement, 1 g of the sample was weighed, placed in 10 g of PGMEA and stirred for 3 hours using a shaker. The resulting mixture was centrifuged at 3500 rpm for 5 minutes using a centrifuge, and the supernatant was filtered using a 0.2 mu m syringe filter. The solids content of 1 g of the filtered solution was measured at 180 캜 for 60 minutes using a moisture analyzer. Solubility calculations are performed based on the measurement results. The equation is as follows.
Solubility (%) = (sample weight after drying / sample weight before drying) x 100
According to the results shown in Table 1, it can be seen that the compound according to the present invention has a remarkably improved solubility in PGMEA.
<Experimental Example 2: Reliability Evaluation
Heat resistance measurement
For the measurement of the heat resistance, the resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on a glass substrate of 10 cm x 10 cm in thickness of 2 mu m and pre-baked on a hot plate at 90 DEG C for 3 minutes And then cooled at room temperature for 1 minute. This was exposed using an exposure machine at an exposure amount of 100 mJ / cm 2 (based on 365 nm).
After post-baking in a convection oven at 230 ° C for 30 minutes, color characteristics were confirmed using a spectrophotometer, MCPD 3700 from Otsuka electronic Co., After the heat treatment, the color characteristic was confirmed again, and the value of? Eab * was obtained
Are shown in Table 2 below.
The value of DELTA Eab * is preferably 3 or less, and the smaller the value is, the higher the heat resistance is.
Light resistance Measure
After the spin coating, exposure and post-baking were carried out in the same manner as in the measurement of heat resistance, the color characteristics were confirmed using a spectrophotometer, MCPD3700 manufactured by Otsuka electronic Co., Ltd., and 1.34 W / m 2 / And the color characteristic was confirmed again, and the value of [Delta] Eab * was obtained, and it is shown in Table 2 below.
The value of DELTA Eab * is preferably 3 or less, and the smaller the value, the greater the light resistance.
<Experimental Example 3> Evaluation of fluorescence
For fluorescence evaluation, 0.1 g of the sample was added to MC (Methylene Chloride) and diluted 1000 times. One ml of the sample was diluted 500 times with MC, and fluorescence was measured using a LS 45 Luminescence Spectrometer of Perkin Elmer.
ΔEab *
According to the results of Table 2, it can be seen that the compound according to the present invention has improved fluorescence and heat resistance.
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 (9)
(2)
In Formula 2,
R1 and R2 are
R11, R12, R13 and R14 each independently represent a substituent selected from a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, and an ester group having 1 to 10 carbon atoms, At least one of R13, R14 and R14 is different from the rest by the kind of the substituent or the position of the substituent, and at least one substituent of R11, R12, R13 and R14 is substituted at the para or meta position,
Two or more substituents of R11, R12, R13 and R14 are halogen atoms, and when any two substituents are halogen atoms, the kinds of these halogen atoms are the same and the remaining substituents are straight or branched alkyl groups having 1 to 10 carbon atoms ; When any three kinds of substituents are halogen atoms, the kinds of these halogen atoms are the same and the remaining substituents are selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, and an ester group having 1 to 10 carbon atoms Lt; / RTI > When all four substituents are halogen atoms, the kind of halogen atoms of the three substituents is the same,
Y1, Y2, Y3 and Y4 are each independently an oxygen (O) atom or a sulfur (S)
a, b, c and d each independently represents an integer of 1 or 2,
R21 to R25 each independently represent a substituent selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.
[Formula 3-1]
[Formula 3-2]
[Formula 3-3]
[Chemical Formula 3-4]
[Formula 3-5]
[Chemical Formula 3-6]
[Chemical Formula 3-7]
[Chemical Formula 3-8]
[Chemical Formula 3-9]
[Chemical Formula 3-10]
[Formula 3-11]
(3-12)
Adding at least two kinds of phenol compound solutions dissolved in the same reaction solvent as the reaction solvent and potassium carbonate at the reaction temperature; And
A process for producing a perylene bisimide compound according to claim 2 or 5, which comprises cooling the reaction solution to room temperature, discharging it to distilled water, and filtering under reduced pressure.
[Chemical Formula 4]
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| PCT/KR2017/002421 WO2018147496A1 (en) | 2017-02-07 | 2017-03-07 | Perylene bisimide-based compound and dye containing same |
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| KR101992084B1 (en) * | 2019-02-21 | 2019-06-21 | 동우 화인켐 주식회사 | A self emission type composition, a color conversion layer manufactured by using thereof and a color filter comprising the color conversion layer and display device |
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| US4845223A (en) * | 1985-12-19 | 1989-07-04 | Basf Aktiengesellschaft | Fluorescent aryloxy-substituted perylene-3,4,9,10-tetracarboxylic acid diimides |
| JP3104223B2 (en) * | 1997-11-06 | 2000-10-30 | 日本電気株式会社 | Organic electroluminescent device |
| JP6456302B2 (en) * | 2013-02-11 | 2019-01-23 | フィリップス ライティング ホールディング ビー ヴィ | Phenoxy-substituted perylene-3,4,9,10-tetracarboxylic acid diimide organic red emitter and light emitting device using the same |
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