KR102618706B1 - Perylene bisimide based compounds and dyes comprising the same - Google Patents

Abstract

The present invention provides a perylene bisimide-based compound represented by the following formula (1), which not only has excellent solubility in organic solvents, especially propylene glycol monomethyl ether acetate (PGMEA), but also provides a dye with little fluorescence decrease at high temperatures. to provide:
[Formula 1]

In Formula 1, R ₁ to R ₄ , x, y and z are the same as defined in the detailed description of the invention.

Description

Perylene bisimide-based compounds and dyes containing them {PERYLENE BISIMIDE BASED COMPOUNDS AND DYES COMPRISING THE SAME}

The present invention relates to a compound containing a perylene bisimide structure, a dye containing the same, a colored resin composition containing such a dye, and a display device using such a colored resin composition.

As a flat panel display device, a liquid crystal display device has been widely used until recently. Liquid crystal display devices require a backlight as a separate light source and have technical limitations in brightness and contrast ratio. Recently, in accordance with the trend of enlarging screens and minimizing thickness, display devices have been equipped with organic light emitting devices (OLED) that are self-luminous, do not require a separate light source, and have fast response speeds, wide viewing angles, and high contrast ratios. Interest in this is increasing.

There are two ways to implement color in OLED: the RGB (Red Green Blue) method and the W-OLED (White Organic Light Emitting Diodes) method. The RGB method does not require a color filter because each red (R), green (G), or blue (B) pixel emits light of the corresponding color, and the light from the OLED itself is transmitted as is, so brightness does not decrease. Although there are advantages, since a fine metal mask (FMM) is used when depositing organic materials, the center of the fine metal mask sags when enlarged, which reduces the process yield and makes it difficult to apply to large TVs. There is a downside. Therefore, the W-OLED method is being proposed as an alternative to the RGB method.

In the W-OLED method, white (W) light emitted from the emitting layer is filtered as it passes through the color filter layer, and each pixel emits red (R), green (G), or blue (B) light to create a full-color image. displays. Since the W-OLED method does not require the use of a fine metal mask, it is an advantageous technology for mass production as it is easy to enlarge and process. However, because a color filter is used, the luminance and color gamut are inevitably lower than that of RGB OLED.

In the case of W-OLED, there is a difference in intensity in the order of blue light > green light > red light. If the intensity of the green (G) and red (R) regions of the light source is supplemented, luminance and color reproduction can be improved. For this reason, the method of introducing a color conversion layer (CCL) using fluorescent dyes has recently been attracting attention.

Specifically, as shown in Figure 1, a color conversion layer is applied between the W-OLED layer and the color filter layer, and the fluorescent dye is excited by the blue light and green light from the light source to emit green light and red light, thereby increasing the luminous efficiency of the green and red pixels. By improving it, not only luminance but also color gamut can be improved (International Display Workshops 2018 (IDW'18), Study of Viewing Angle on Fluorescence Dye Photo Resist for OLED Display, P675-678).

In order to apply the color conversion layer in the form shown in Figure 1, the color conversion layer process must be performed before the color filter (R, G, B) process. In the case of the color filter process, there is a baking process for each color of R, G, and B, so the fluorescent dye applied in the color conversion layer process must have excellent heat resistance, and the fluorescence (fluorescence) at high temperature during the color conversion layer application process. It can be applied only when there is a small decrease in fluorescent intensity. Recently, several studies have been conducted using fluorescent dyes, and in particular, studies have been conducted on perylene-based dyes with excellent high-temperature stability. However, in the case of perylene dyes, it is not easy to secure solubility in organic solvents due to intermolecular arrangement due to intermolecular π-π interaction, and even when solubility in organic solvents is secured, the resin containing the dye After manufacturing the composition, aggregation occurs during high-temperature baking during the color conversion layer manufacturing process, resulting in a significant decrease in fluorescence, making application difficult.

The problem to be solved by the present invention is to provide a perylene bisimide-based compound with high solubility in organic solvents, and also to provide a perylene bisimide-based compound with low fluorescence reduction due to high-temperature baking when applying a color conversion layer after manufacturing a resin composition. Providing a compound.

Another object of the present invention is to provide a dye mixture and resin composition containing the perylene bisimide-based compound, and a display device using the dye mixture and resin composition.

In order to solve the problems of the present invention, a perylene bisimide-based compound represented by the following formula (1) is provided:

[Formula 1]

In Formula 1,

R ₁ is 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl,

R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl group with 1 to 18 carbon atoms, a haloalkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, an aralkyl group with 6 to 18 carbon atoms, and a carbon atom group with 1 to 18 carbon atoms. It is an alkoxy group, a heterocyclic group having 3 to 30 ring atoms, or a halogen,

x, y and z are each integers from 0 to 5, and when x, y or z is 2 to 5, each R ₂ , R ₃ or R ₄ may be the same or different,

The heterocyclic group includes one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P.

The perylene bisimide-based compound according to the present invention has excellent solubility in organic solvents, making it easy to manufacture a resin composition containing it, and when applying a color conversion layer, there is little decrease in fluorescence even after high-temperature baking, enabling improvement in brightness and color reproduction rate. do.

Figure 1 shows a W-OLED structure in which a color conversion layer (CCL) is applied between the W-OLED layer and the color filter layer.

Hereinafter, the present invention will be described in more detail.

If you check the light source spectrum of the W-OLED display, there is a difference in intensity in the order of blue light > green light > red light. By compensating for the relatively weak intensity of green light and red light in the spectrum, it is possible to improve luminance and color gamut. For this reason, the method of introducing a color conversion layer using fluorescent dyes has recently been attracting attention.

The fluorescent dye in the color conversion layer is excited by the blue light and green light emitted from the W-OLED (light source) and emits green light and red light, thereby improving the luminous efficiency of the green and red pixels, thereby improving luminance as well as color reproduction rate.

The method of applying fluorescent dye to the color conversion layer is similar to the method of applying color filters by manufacturing it in the form of a resin composition and coating it, so the solubility of the fluorescent dye in the organic solvent is important. In addition, after coating the resin composition, high-temperature drying is performed to remove residual solvents and cure, so if the fluorescence of the fluorescent dye is reduced by high-temperature drying, it cannot be applied to the color conversion layer.

However, previously known fluorescent dyes may not be soluble in propylene glycol monomethyl ether acetate (PGMEA) or may have low solubility, and even after ensuring solubility, fluorescence is reduced during high-temperature baking when applied to the color conversion layer after manufacturing the resin composition. There is a problem.

In order to improve this problem, the present inventors carefully examined the possibility of improving solubility according to the structure of fluorescent dyes, and found that perylene bisimide-based compounds with specific substituents have excellent solubility in organic solvents, especially PGMEA.

Accordingly, the present invention provides a perylene bisimide-based compound that is easy to manufacture, has high solubility in PGMEA, and does not significantly reduce fluorescence even at high temperatures when applying a color conversion layer after manufacturing a resin composition.

Specifically, the present invention provides a perylene bisimide-based compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ is 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl,

R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl group with 1 to 18 carbon atoms, a haloalkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, an aralkyl group with 6 to 18 carbon atoms, and a carbon atom group with 1 to 18 carbon atoms. It is an alkoxy group, a heterocyclic group having 3 to 30 ring atoms, or a halogen,

x, y and z are each integers from 0 to 5, and when x, y or z is 2 to 5, each R ₂ , R ₃ or R ₄ may be the same or different,

The heterocyclic group includes one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P.

According to one embodiment, in the perylene bisimide-based compound represented by Formula 1, R ₂ , R ₃ and R ₄ may be substituted at one or more of the ortho, para and meta positions. You can.

According to one embodiment, in the perylene bisimide-based compound represented by Formula 1, R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl group with 1 to 8 carbon atoms, a haloalkyl group with 1 to 4 carbon atoms, and a carbon number An aryl group with 6 to 10 carbon atoms, an aralkyl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a heterocyclic group with 9 to 12 ring atoms, F, Cl or Br, where the heterocyclic group is fused to a benzene ring. , N and S, and contains two or more identical or different heteroatoms.

According to one embodiment, in the perylene bisimide-based compound represented by Formula 1, x, y, and z are each integers of 0 to 3, and when x, y, or z is 2 or 3, each R ₂ , R ₃ or R ₄ may be the same or different.

As used herein, “alkyl group having 1 to 18 carbon atoms” refers to straight or branched chain alkyl having 1 to 18 carbon atoms, and specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. , t-butyl, isobutyl, t-butyl, n-amyl, t-amyl, t-octyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, etc.

As used herein, “haloalkyl group having 1 to 18 carbon atoms” refers to alkyl in which one or more hydrogens of the alkyl group are replaced with halogen, and specific examples of haloalkyl include fluoromethyl, fluoroethyl, chloromethyl, chloroethyl, These include trichloromethyl, trifluoromethyl, and nonafluorobutyl.

As used herein, “aralkyl group having 6 to 18 carbon atoms” refers to a monovalent radical in which one or more hydrogens of the alkyl group are replaced with an aryl group, and specific examples of aralkyl include benzyl, phenylethyl, methylbenzyl, naphthylmethyl, Butylphenyl, etc.

As used herein, “aryl group having 6 to 18 carbon atoms” refers to a single ring or fused ring radical derived from an aromatic hydrocarbon having 6 to 18 carbon atoms, and examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, These include fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, chrysenyl, naphthacenyl, and fluoranthenyl.

As used herein, “alkoxy group having 1 to 18 carbon atoms” means straight or branched chain alkoxy having 1 to 18 carbon atoms, and examples of such alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, 1 -Ethylpropoxy, hexyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, methoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy. , 2-butoxyethoxy, etc.

As used herein, “heterocyclic group having 3 to 30 ring atoms” refers to a group having 3 to 30 ring skeleton atoms and one or more heteroatoms selected from the group consisting of B, N, O, S, P(=O), Si, and P. It means an aryl group containing. Here, the number of ring skeleton atoms is preferably 3 to 20, and more preferably 3 to 15. The number of heteroatoms is preferably 1 to 4, and may be a single ring system or a fused ring system condensed with one or more benzene rings, and may be partially saturated. The heterocyclic group also includes one or more heteroaryl groups or forms in which an aryl group is connected to a heteroaryl group by a single bond. Examples of the heterocyclic group include furyl, tetrahydrofurfuryl, pyranyl, tetrahydropyranyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothia. Single ring heterocyclic groups such as zolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, or benzoyl. furanyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzotriazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, Isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. There is a fused ring system heterocycle.

As used herein, “halogen” includes F, Cl, Br and I atoms.

According to one embodiment, the perylene bisimide-based compound represented by Formula 1 may be selected from the group consisting of compounds of the following Formulas 1 to 77, but is not limited thereto:

The perylene bisimide-based compound according to the present invention can be prepared by synthetic methods known to those skilled in the art, for example,

Dissolving a compound of the following formula (2) or a compound of the formula (3), a phenolic compound, and potassium carbonate in a solvent and then raising the temperature;

Cooling the reaction mixture to room temperature and filtering the resulting compound; and

It can be prepared by a method comprising dissolving the filtered compound in a solvent, concentrating the organic layer under reduced pressure, and then drying it in vacuum:

[Formula 2]

[Formula 3]

According to one embodiment, the phenol-based compound is 4-cumylphenol, or in addition to 4-cumylphenol, an alkyl group with 1 to 8 carbon atoms, a haloalkyl group with 1 to 4 carbon atoms, and an aryl group with 6 to 10 carbon atoms. It may include one or more phenols substituted or unsubstituted with an aralkyl group having 6 to 10 carbon atoms, F, Cl, Br, benzotriazole, benzothiazole, or an alkoxy group having 1 to 4 carbon atoms.

According to one embodiment, the phenol-based compound may be added in an excess molar content relative to the compound of Formula 2 or the compound of Formula 3. The phenol-based compound and the compound of Formula 2 or the compound of Formula 3 may be added, for example, at a molar ratio of 4:1 to 6:1, and more preferably at a molar ratio of 4:1 to 5.5:1. may be added.

According to one embodiment, the temperature increase temperature may be 60 to 150°C, for example, 135 to 145°C.

According to one embodiment, the solvent is N-methyl-2-pyrrolidone (NMP), chloroform (CHCl ₃ ), acetone, acetonitrile, sulfolane, dimethylsulfoxide, dimethylformamide ( DMF), dichloroethane, dimethylacetamide (DMAC), 1,4-dioxane, tetrahydrofuran (THF), toluene, xylene, chlorobenzene, o-dichlorobenzene, etc. can be selected

The present invention also provides a dye containing the perylene bisimide-based compound.

The present invention also provides a colored resin composition containing the above dye.

The present invention further provides a display device using the colored resin composition.

Hereinafter, for a detailed understanding of the present invention, the compounds according to the present invention will be described in more detail by citing representative compounds of the present invention. However, these examples are for illustrating the present invention in more detail, and the scope of the present invention is not limited thereto, and it is common knowledge in the art that various changes and modifications are possible within the scope and technical spirit of the present invention. It will be self-evident to those who have it.

<Preparation Example 1> Synthesis of Intermediate 1

0.05 mol (26.50 g) of 1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride and 2,6-diisopropylaniline (2, 0.125 mol (22.16 g) of 6-diisopropylaniline) was added to 250 g of propionic acid, a reflux device was connected, and the reaction mixture was heated to 140°C and refluxed. After 24 hours, the reaction mixture was cooled to room temperature, filtered, washed with 50 g of methanol and 150 g of ultrapure water, and dried under vacuum. The dried compound was purified by column chromatography (solvent: methylene chloride (MC):hexane (Hex) = 1:1) to obtain 32.25 g of Intermediate 1. MS analysis: m/z 846

<Preparation Example 2> Synthesis of Intermediate 2

0.050 mol (26.50 g) of 1,6,7,12-tetrachloroperylene tetracarboxylic dianhydride and 0.125 mol (16.90 g) of 2,4,6-trimethylaniline (2,4,6-trimethylaniline) were mixed with propionic acid. 250 g was added, a reflux device was connected, and the reaction mixture was heated to 140°C and refluxed. After 24 hours, the reaction mixture was cooled to room temperature, filtered, washed with 50 g of methanol and 150 g of ultrapure water, and dried under vacuum. The dried compound was purified by column chromatography (solvent: MC:Hex = 1:1) to obtain 25.99 g of Intermediate 2. MS analysis: m/z 762

<Example 1> Preparation of compound of formula 1

0.04 mol (8.49 g) of 4-cumylphenol, 0.04 mol (5.53 g) of K ₂ CO ₃ and 50 g of DMF were added to 0.01 mol (8.46 g) of Intermediate 1 compound prepared in Preparation Example 1, and the temperature was raised to 140°C. and reacted for 24 hours. After the reaction mixture was cooled to room temperature, it was added dropwise to 200 g of H ₂ O, and the obtained compound was filtered. The filtered compound was dissolved in 100 g of CHCl ₃ , washed with 100 g of water, and the organic layer was concentrated under reduced pressure, dried in vacuum, and purified by column chromatography (solvent: MC:Hex = 1:2) to obtain the compound of Formula 1. 7.31g was obtained. MS analysis: m/z 1550

<Example 2> Preparation of compound of formula 2

To 0.01 mol (8.46 g) of the intermediate 1 compound prepared in Preparation Example 1, 0.02 mol (4.25 g) of 4-cumylphenol, 0.02 mol (1.88 g) of phenol, 0.04 mol (5.53 g) of K ₂ CO ₃ and 50 g of DMF were added. After addition, the temperature was raised to 140°C and reaction was performed for 24 hours. After the reaction mixture was cooled to room temperature, it was added dropwise to 200 g of H ₂ O, and the obtained compound was filtered. The filtered compound was dissolved in 100 g of CHCl ₃ , washed with 100 g of water, and the organic layer was concentrated under reduced pressure, dried in vacuum, and purified by column chromatography (solvent: MC:Hex = 1:5) to obtain the compound of Formula 2. 6.17g was obtained. MS analysis: m/z 1314

<Example 3> Preparation of compound of formula 3

To 0.01 mol (8.46 g) of the intermediate 1 compound prepared in Preparation Example 1, 0.03 mol (6.37 g) of 4-cumylphenol, 0.01 mol (0.94 g) of phenol, 0.04 mol (5.53 g) of K ₂ CO ₃ and 50 g of DMF were added. After addition, the temperature was raised to 140°C and reaction was performed for 24 hours. After the reaction mixture was cooled to room temperature, it was added dropwise to 200 g of H ₂ O, and the obtained compound was filtered. The filtered compound was dissolved in 100 g of CHCl ₃ , washed with 100 g of water, and the organic layer was concentrated under reduced pressure, dried in vacuum, and purified by column chromatography (solvent: MC:Hex = 1:2) to obtain the compound of Formula 3. 7.70g was obtained. MS analysis: m/z 1432

<Examples 4 to 77> Preparation of compounds of formulas 4 to 77

Compounds of Formulas 4 to 77 described above were prepared in the same manner as in Examples 1 to 3, except for using the types and amounts of intermediates and phenolic compounds shown in Table 1 below.

Example intermediate phenolic compounds product M.S. 4 1 0.01mol 4-cumylphenol 0.01mol
p-cresol 0.03mol Formula 4 1238 5 1 0.01mol 4-cumylphenol 0.02mol
p-cresol 0.02mol Formula 5 1342 6 1 0.01mol 4-cumylphenol 0.03mol
p-cresol 0.01mol Formula 6 1446 7 1 0.01mol 4-cumylphenol 0.01mol
4-t-butylphenol 0.03mol Formula 7 1364 8 1 0.01mol 4-cumylphenol 0.02mol
4-t-butylphenol 0.02mol Formula 8 1426 9 1 0.01mol 4-cumylphenol 0.03mol
4-t-butylphenol 0.01mol Formula 9 1488 10 1 0.01mol 4-cumylphenol 0.01mol
4-t-octylphenol 0.03mol Formula 10 1532 11 1 0.01mol 4-cumylphenol 0.02mol
4-t-octylphenol 0.02mol Formula 11 1538 12 1 0.01mol 4-cumylphenol 0.03mol
4-t-octylphenol 0.01mol Formula 12 1544 13 1 0.01mol 4-cumylphenol 0.01mol
2,4-dimethylphenol 0.03mol Formula 13 1280 14 1 0.01mol 4-cumylphenol 0.02mol
2,4-dimethylphenol 0.02mol Formula 14 1370 15 1 0.01mol 4-cumylphenol 0.03mol
2,4-dimethylphenol 0.01mol Formula 15 1460 16 1 0.01mol 4-cumylphenol 0.01mol
2,5-dimethylphenol 0.03mol Formula 16 1280 17 1 0.01mol 4-cumylphenol 0.02mol
2,5-dimethylphenol 0.02mol Formula 17 1370 18 1 0.01mol 4-cumylphenol 0.03mol
2,5-dimethylphenol 0.01mol Formula 18 1460 19 1 0.01mol 4-cumylphenol 0.01mol
4-phenylphenol 0.03mol Formula 19 1424 20 1 0.01mol 4-cumylphenol 0.02mol
4-phenylphenol 0.02mol Formula 20 1466 21 1 0.01mol 4-cumylphenol 0.03mol
4-phenylphenol 0.01mol Formula 21 1508 22 1 0.01mol 4-cumylphenol 0.01mol
4-Benzylphenol 0.03mol Formula 22 1466 23 1 0.01mol 4-cumylphenol 0.02mol
4-Benzylphenol 0.02mol Formula 23 1496 24 1 0.01mol 4-cumylphenol 0.03mol
4-Benzylphenol 0.01mol Formula 24 1522 25 1 0.01mol 4-cumylphenol 0.01mol
4-fluorophenol 0.03mol Formula 25 1250 26 1 0.01mol 4-cumylphenol 0.02mol
4-fluorophenol 0.02mol Formula 26 1350 27 1 0.01mol 4-cumylphenol 0.03mol
4-fluorophenol 0.01mol Formula 27 1450 28 1 0.01mol 4-cumylphenol 0.01mol
4-chlorophenol 0.03mol Formula 28 1298 29 1 0.01mol 4-cumylphenol 0.02mol
4-chlorophenol 0.02mol Formula 29 1382 30 1 0.01mol 4-cumylphenol 0.03mol
4-chlorophenol 0.01mol Formula 30 1466 31 1 0.01mol 4-cumylphenol 0.01mol
4-bromophenol 0.03mol Formula 31 1430 32 1 0.01mol 4-cumylphenol 0.02mol
4-bromophenol 0.02mol Formula 32 1470 33 1 0.01mol 4-cumylphenol 0.03mol
4-bromophenol 0.01mol Formula 33 1510 34 1 0.01mol 4-cumylphenol 0.02mol
2,5-dichlorophenol 0.02mol Formula 34 1450 35 1 0.01mol 4-cumylphenol 0.03mol
2,5-dichlorophenol 0.01mol Formula 35 1500 36 1 0.01mol 4-cumylphenol 0.01mol
2,4-di-t-butylphenol 0.03mol Formula 36 1532 37 1 0.01mol 4-cumylphenol 0.02mol
2,4-di-t-butylphenol 0.02mol Formula 37 1538 38 1 0.01mol 4-cumylphenol 0.03mol
2,4-di-t-butylphenol 0.01mol Formula 38 1544 39 1 0.01mol 4-cumylphenol 0.02mol
2-(2H-benzotriazol-2-yl)-p-cresol 0.02 mol Formula 39 1577 40 1 0.01mol 4-cumylphenol 0.03mol
2-(2H-benzotriazol-2-yl)-p-cresol 0.01 mol Formula 40 1563 41 1 0.01mol 4-cumylphenol 0.02mol
2-(2-hydroxyphenyl)benzothiazole 0.02mol Formula 41 1581 42 1 0.01mol 4-cumylphenol 0.03mol
2-(2-hydroxyphenyl)benzothiazole 0.01mol Formula 42 1579 43 2 0.01mol 4-cumylphenol 0.01mol
4-fluorophenol 0.03mol Formula 43 1166 44 2 0.01mol 4-cumylphenol 0.02mol
4-fluorophenol 0.02mol Formula 44 1266 45 2 0.01mol 4-cumylphenol 0.03mol
4-fluorophenol 0.01mol Formula 45 1366 46 2 0.01mol 4-cumylphenol 0.02mol
4-chlorophenol 0.02mol Formula 46 1298 47 2 0.01mol 4-cumylphenol 0.03mol
4-chlorophenol 0.01mol Formula 47 1382 48 2 0.01mol 4-cumylphenol 0.03mol
4-bromophenol 0.01mol Formula 48 1426 49 2 0.01mol 4-cumylphenol 0.04mol Formula 49 1466 50 2 0.01mol 4-cumylphenol 0.03mol
4-t-butylphenol 0.01mol Formula 50 1404 51 2 0.01mol 4-cumylphenol 0.02mol
4-t-butylphenol 0.02mol Formula 51 1342 52 2 0.01mol 4-cumylphenol 0.02mol
p-cresol 0.02mol Formula 52 1258 53 2 0.01mol 4-cumylphenol 0.03mol
p-cresol 0.01mol Formula 53 1362 54 2 0.01mol 4-cumylphenol 0.03mol
4-t-octylphenol 0.01mol Formula 54 1460 55 2 0.01mol 4-cumylphenol 0.02mol
4-t-octylphenol 0.02mol Formula 55 1454 56 2 0.01mol 4-cumylphenol 0.03mol
2,4-di-t-butylphenol 0.01mol Formula 56 1460 57 2 0.01mol 4-cumylphenol 0.02mol
2,4-di-t-butylphenol 0.02mol Formula 57 1454 58 2 0.01mol 4-cumylphenol 0.01mol
4-Benzylphenol 0.03mol Formula 58 1382 59 2 0.01mol 4-cumylphenol 0.03mol
2,4-dimethylphenol 0.01mol Formula 59 1376 60 2 0.01mol 4-cumylphenol 0.01mol
2,5-dimethylphenol 0.03mol Formula 60 1196 61 2 0.01mol 4-cumylphenol 0.03mol
4-phenylphenol 0.01mol Formula 61 1424 62 2 0.01mol 4-cumylphenol 0.02mol
4-phenylphenol 0.02mol Formula 62 1382 63 2 0.01mol 4-cumylphenol 0.03mol
3-trifluoromethylphenol
0.01mol Formula 63 1416 64 2 0.01mol 4-cumylphenol 0.03mol
2-(2H-benzotriazol-2-yl)-p-cresol 0.01 mol Formula 64 1479 65 2 0.01mol 4-cumylphenol 0.02mol
2-(2-hydroxyphenyl)benzothiazole 0.02mol Formula 65 1497 66 1 0.01mol 4-cumylphenol 0.03mol
2-methoxyphenol 0.01mol Formula 66 1462 67 1 0.01mol 4-cumylphenol 0.02mol
2-methoxyphenol 0.02mol Formula 67 1374 68 2 0.01mol 4-cumylphenol 0.03mol
3-methoxyphenol 0.01mol Formula 68 1378 69 1 0.01mol 4-cumylphenol 0.02mol
3-methoxyphenol 0.02mol Formula 69 1374 70 1 0.01mol 4-cumylphenol 0.01mol
p-cresol 0.02mol
Phenol 0.01mol Formula 70 1224 71 2 0.01mol 4-cumylphenol 0.02mol
4-t-butylphenol 0.01mol
Phenol 0.01mol Formula 71 1286 72 1 0.01mol 4-cumylphenol 0.02mol
p-cresol 0.01mol
4-chlorophenol 0.01mol Formula 72 1362 73 1 0.01mol 4-cumylphenol 0.01mol
p-cresol 0.02mol
4-phenylphenol 0.01mol Formula 73 1300 74 1 0.01mol 4-cumylphenol 0.02mol
4-Benzylphenol 0.01mol
p-cresol 0.01mol Formula 74 1418 75 2 0.01mol 4-cumylphenol 0.02mol
3-methoxyphenol 0.01mol
p-cresol 0.01mol Formula 75 1274 76 1 0.01mol 4-cumylphenol 0.01mol
4-t-butylphenol 0.01mol
2,5-dimethylphenol 0.01mol
Phenol 0.01mol Formula 76 1280 77 2 0.01mol 4-cumylphenol 0.01mol
4-t-butylphenol 0.01mol
4-t-octylcresol 0.01mol
p-cresol 0.01mol Formula 77 1294

<Comparative Example 1> Preparation of compound of formula 78

0.04 mol (4.70 g) of phenol, 0.04 mol (5.53 g) of K ₂ CO ₃ and 50 g of DMF were added to 0.01 mol (8.46 g) of Intermediate 1 compound prepared in Preparation Example 1, then heated to 140°C and incubated for 24 hours. It was allowed to react for a while. After the reaction mixture was cooled to room temperature, it was added dropwise to 200 g of H ₂ O, and the obtained compound was filtered. The filtered compound was dissolved in 100 g of CHCl ₃ , washed with 100 g of water, and the organic layer was concentrated under reduced pressure, dried in vacuum, and purified by column chromatography (solvent: MC:Hex = 1:3) to obtain the compound of Formula 78. 6.42g was obtained. MS: 1079

<Comparative Example 2> Preparation of the compound of Formula 79

After adding 0.04 mol (4.70 g) of phenol, 0.04 mol (5.53 g) of K ₂ CO ₃ and 50 g of DMF to 0.01 mol (7.64 g) of the intermediate 2 compound prepared in Preparation Example 2, the temperature was raised to 140°C and incubated for 24 hours. It was allowed to react for a while. The reaction mixture was cooled to room temperature, then added dropwise to 200 g of H ₂ O, and the obtained compound was filtered. The filtered compound was dissolved in 100 g of CHCl ₃ , washed with 100 g of water, and the organic layer was concentrated under reduced pressure, dried in vacuo, and purified by column chromatography (solvent: MC:Hex = 1:3) to obtain the compound of Formula 79. Got 5.95g. MS: 994

<Experimental Example 1> Solubility evaluation

Solubility was measured by dissolving the dye compounds of Comparative Examples 1 and 2 and the dye compounds of Examples 1 to 77, respectively, in propylene glycol monomethyl ether acetate (PGMEA), and the results are shown in Table 2 below.

PGMEA
solubility PGMEA
Solubility PGMEA
solubility Comparative Example 1 >1% Example 26 >5% Example 53 >5% Comparative Example 2 <1% Example 27 >5% Example 54 >5% Example 1 >5% Example 28 >3% Example 55 >5% Example 2 >5% Example 29 >5% Example 56 >5% Example 3 >5% Example 30 >5% Example 57 >5% Example 4 >5% Example 31 >3% Example 58 >5% Example 5 >5% Example 32 >5% Example 59 >5% Example 6 >5% Example 33 >5% Example 60 >3% Example 7 >5% Example 34 >3% Example 61 >5% Example 8 >5% Example 35 >5% Example 62 >5% Example 9 >5% Example 36 >10% Example 63 >5% Example 10 >5% Example 37 >10% Example 64 >3% Example 11 >5% Example 38 >5% Example 65 >1% Example 12 >5% Example 39 >3% Example 66 >5% Example 13 >5% Example 40 >5% Example 67 >5% Example 14 >5% Example 41 >3% Example 68 >5% Example 15 >5% Example 42 >5% Example 69 >5% Example 16 >5% Example 43 >3% Example 70 >5% Example 17 >5% Example 44 >5% Example 71 >5% Example 18 >5% Example 45 >5% Example 72 >5% Example 19 >3% Example 46 >1% Example 73 >5% Example 20 >5% Example 47 >5% Example 74 >5% Example 21 >5% Example 48 >5% Example 75 >5% Example 22 >5% Example 49 >5% Example 76 >5% Example 23 >5% Example 50 >5% Example 77 >5% Example 24 >5% Example 51 >5% Example 25 >5% Example 52 >3%

As a result of solubility measurement in PGMEA, the dye compounds of Examples 1 to 77 showed higher solubility than the dye compounds of Comparative Examples 1 and 2.

<Manufacture of resin composition>

Resin compositions containing the dye compounds of Examples 1 to 77 and Comparative Examples 1 and 2, respectively, were prepared in the following manner.

1.4 g of benzyl methacrylate/methacrylic acid (mass ratio 60:40) copolymer (Mw=20000) as a binder resin, 5.0 g of dipentaerythritol hexaacrylate as an acrylic monomer, the dye compounds of Examples 1 to 77, and 0.5 g each of the dye compounds of Comparative Examples 1 and 2, 1.0 g of Irgacure OXE-02 (BASF) as a photopolymerization initiator, and 42.1 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed and stirred for 2 hours to mix each resin. A sample of the composition was prepared.

<Experimental Example 2> Measurement of fluorescence intensity reduction rate

To measure the fluorescence reduction rate, each resin composition sample prepared as above was spin-coated to a thickness of 3㎛ on a 10cm × 10cm glass substrate and pre-baked for 3 minutes on a hot plate at 90°C. After performing this, it was cooled at room temperature for 1 minute. This was exposed using DYMAX 5000-EC (Dymax Corporation).

Afterwards, postbaking was performed in a convection oven at 230°C for 20 minutes, and the initial fluorescence was measured using a LS 45 Fluorescence Spectrometer (Perkin Elmer). Afterwards, the fluorescence was measured again by additional baking at 230°C for 1 hour, and the fluorescence reduction rate was calculated from the fluorescence measurement results before and after additional baking. The results are shown in Table 3 below.

initial fluorescence Fluorescence
decline rate initial fluorescence Fluorescence
decline rate Comparative Example 1 3152 61.5% Example 39 3348 19.8% Comparative Example 2 Test not possible (solubility <1%) Example 40 1.97 23.8% Example 1 3410 11.2% Example 41 3535 8.4% Example 2 3727 16.0% Example 42 3723 12.6% Example 3 3615 18.5% Example 43 3811 4.3% Example 4 3619 12.6% Example 44 3569 7.0% Example 5 3812 10.6% Example 45 3738 7.7% Example 6 3147 20.1% Example 46 3034 15.3% Example 7 3503 8.3% Example 47 3686 7.9% Example 8 3311 11.0% Example 48 3227 20.0% Example 9 3042 15.3% Example 49 3876 22.5% Example 10 4120 8.4% Example 50 4093 8.1% Example 11 3899 18.7% Example 51 3703 23.7% Example 12 3811 20.6% Example 52 3322 14.3% Example 13 3810 12.1% Example 53 3398 16.1% Example 14 3187 13.7% Example 54 3697 10.7% Example 15 3422 9.3% Example 55 4087 10.9% Example 16 3918 20.5% Example 56 3893 12.1% Example 17 3616 16.1% Example 57 3891 19.1% Example 18 3711 7.1% Example 58 3563 4.9% Example 19 3496 23.5% Example 59 3601 6.1% Example 20 3387 17.6% Example 60 3790 21.8% Example 21 3184 11.6% Example 61 3921 6.2% Example 22 3095 14.8% Example 62 3369 13.4% Example 23 3129 10.4% Example 63 3516 10.0% Example 24 3865 8.7% Example 64 3511 4.7% Example 25 3453 12.5% Example 65 3229 17.0% Example 26 4035 23.4% Example 66 4142 14.4% Example 27 4012 21.5% Example 67 3797 20.8% Example 28 2983 17.4% Example 68 3807 9.2% Example 29 3172 5.0% Example 69 3596 8.5% Example 30 3475 6.6% Example 70 4092 12.3% Example 31 3180 4.2% Example 71 3885 13.9% Example 32 4187 19.9% Example 72 4124 11.7% Example 33 3855 22.6% Example 73 4095 8.3% Example 34 3046 7.1% Example 74 3815 17.8% Example 35 3260 5.4% Example 75 3513 6.5% Example 36 3525 14.7% Example 76 3681 11.3% Example 37 3161 9.6% Example 77 3551 10.1% Example 38 3352 4.0%

As can be seen from Table 3, in the case of Comparative Example 2, the solubility was low at less than 1%, making testing impossible. On the other hand, Comparative Example 1 showed an initial fluorescence somewhat similar to Examples 1 to 77, but after additional baking at 230°C for 1 hour, the fluorescence decrease rate was more than twice that of Examples 1 to 77. . The fluorescent dye compound according to the present invention has high solubility in PGMEA, making it easy to manufacture a resin composition, and is expected to be suitable for application to display devices due to its low fluorescence reduction rate even under high temperature conditions after being coated on an organic substrate.

As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (9)

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

In Formula 1,
R ₁ is 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl,
R ₂ , R ₃ and R ₄ are each independently hydrogen, a straight or branched chain alkyl group with 1 to 18 carbon atoms, a haloalkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, an aralkyl group with 6 to 18 carbon atoms, and a carbon number. It is an alkoxy group of 1 to 18, a heterocyclic group of 3 to 30 ring atoms, or halogen,
x, y and z are each integers from 0 to 5, and when x, y or z is 2 to 5, each R ₂ , R ₃ or R ₄ may be the same or different,
The heterocyclic group includes one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P. The method of claim 1, wherein R ₂ , R ₃ and R ₄ are each independently hydrogen, a straight-chain or branched alkyl group with 1 to 8 carbon atoms, a haloalkyl group with 1 to 4 carbon atoms, an aryl group with 6 to 10 carbon atoms, or a C-6 to 8 alkyl group. an aralkyl group of 10, an alkoxy group of 1 to 4 carbon atoms, a heterocyclic group of 9 to 12 ring atoms, F, Cl or Br, and x, y and z are each integers of 0 to 3, where the heterocyclic group is benzene. A perylene bisimide-based compound comprising two or more identical or different heteroatoms selected from N and S fused to a ring. The perylene bisimide-based compound according to claim 1, wherein the perylene bisimide-based compound represented by Formula 1 is selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 77:

























Dissolving a compound of the following formula (2) or a compound of the formula (3), a phenolic compound, and potassium carbonate in a solvent and then raising the temperature;
Cooling the reaction mixture to room temperature and filtering the resulting compound; and
A method for producing a perylene bisimide-based compound, comprising dissolving the filtered compound in a solvent, concentrating the organic layer under reduced pressure, and then drying it in vacuum:
[Formula 2]

[Formula 3]
The method of claim 4, wherein the phenol-based compound is 4-cumylphenol, or, in addition to 4-cumylphenol, a straight-chain or branched-chain alkyl group with 1 to 8 carbon atoms, a haloalkyl group with 1 to 4 carbon atoms, and 6 carbon atoms. Per, which contains at least one phenol substituted or unsubstituted with an aryl group having 1 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, F, Cl, Br, benzotriazole, benzothiazole, or an alkoxy group having 1 to 4 carbon atoms. Method for producing rylene bisimide-based compounds. The method of claim 4, wherein the solvent is N-methyl-2-pyrrolidone (NMP), chloroform (CHCl ₃ ), acetone, acetonitrile, sulfolane, dimethylsulfoxide, dimethylformamide ( DMF), dichloroethane, dimethylacetamide (DMAC), 1,4-dioxane, tetrahydrofuran (THF), toluene, xylene, chlorobenzene and o-dichlorobenzene. A method for producing a perylene bisimide-based compound selected from the group, wherein the temperature increase temperature is 60 to 150°C. A dye comprising the perylene bisimide-based compound according to any one of claims 1 to 3. A colored resin composition comprising the dye according to claim 7. A display device using the colored resin composition according to claim 8.