WO2018120971A1

WO2018120971A1 - Coumarin green light dye containing triphenylamine ethylene side chain

Info

Publication number: WO2018120971A1
Application number: PCT/CN2017/105310
Authority: WO
Inventors: 周鹏程; 戴雷; 蔡丽菲
Original assignee: 广东阿格蕾雅光电材料有限公司
Priority date: 2016-12-27
Filing date: 2017-10-09
Publication date: 2018-07-05
Also published as: TWI659071B; CN106833009B; TW201823371A; CN106833009A

Abstract

Provided is a coumarin green light dye containing a triphenylamine ethylene side chain. The green light dye has a structure shown in formula (I), wherein R₁, R₂ and R₃ independently represent hydrogen, a C1-C8 substituted or unsubstituted alkyl, alkoxyl or halogen. A molecule having a structure shown in formula (I) has a high fluorescent quantum yield and has a good application potential with regard to light conversion film materials using green light. The material has a strong light-emitting property, is not sensitive to a preparation process and has a very stable emission spectrum in relatively large doping concentration and temperature ranges.

Description

Coumarin-based green dye containing triphenylamine ethylene side chain

Technical field

The invention relates to a novel organic color conversion film material for flat display, in particular to a kind of coumarin-based green light dye containing triphenylamine ethylene side chain, which is formed into a film by solution spin coating, and can be applied to a flat display.

Background technique

With the continuous breakthrough of the display industry technology and the increasing market demand, flat panel displays have emerged rapidly with a series of advantages such as small size, light weight, low power consumption, low radiation, and good electromagnetic compatibility, becoming the mainstream of display technology in the 21st century. . The coloring method of flat panel display plays a very important role in its production process. Its quality directly determines the color rendering effect, production cost and service life of flat panel display.

At present, the mainstream technology for color display of flat panel display is to print red, green and blue fluorescent material preparation devices. However, due to the large difference in lifetime and attenuation of the three primary color fluorescent materials, it is easy to cause color cast of color display, and the three primary colors The manufacturing process of the device is complicated and the cost is high. In order to solve these problems, people have proposed a new idea of color conversion, namely "blue source into color". The "Blue Source into Color" technology uses a blue phosphor with a single high brightness as the backlight. The blue light emitted by the backlight is converted into red and green light after passing through the color conversion film, thereby realizing RGB full color display. This technology not only greatly simplifies the production process of electroluminescent flat panel display, improves the color stability and uniformity of the display, but also significantly reduces the production cost of the display. Materials for color conversion films can be classified into inorganic and organic materials. It has been found that, compared with inorganic phosphors, organic conversion materials not only have higher color conversion efficiency, but also have more saturated colors, so that a wider color gamut can be realized, and raw materials are cheap and easy to obtain, and molecular cutting and modification are easier. For better display.

In the 1990s, the Leising team used the coumarin dye Coumarin 102 as the green light material, and Lumogen F300 used the red dye to disperse in the PMMA to prepare a green and red light conversion film, which achieved a red light conversion efficiency of more than 10%. References: Adv. Mater., 1997, 9(1), 33-36). In recent years, the domestic research team has also reported the preparation of organic light conversion films (Reference: Optoelectronics Letters, 2010, 6 (4), 245-248, CN105267059 A, CN103647003 A), which has obtained a wide color gamut and a light conversion rate. High organic light conversion film. However, these traditional dye molecules are very sensitive to the processing technology. The color of the luminescence will change greatly after processing at different temperatures or after exposure (Reference: Abstract, 2354, 218th ECS Meeting), so the development of environmentally stable light conversion materials is very necessary.

The organic fluorescent color conversion film generally disperses an organic fluorescent dye having different colors uniformly in a polymer solid film by ultraviolet curing or thermal curing, and then excites the organic fluorescent color conversion film with a high-brightness blue backlight. The dye molecules realize the color transition, and the converted red, green and background blue light form the three primary colors of light, and finally Full color display of the electroluminescent element can be achieved.

Summary of the invention

The present invention provides a coumarin-based green light dye molecule having a triphenylamine ethylene side chain, which is dispersed in a polymer resin such as methyl methacrylate (PMMA) to prepare a light conversion. membrane. The material has strong luminescence, is insensitive to the preparation process, and has stable emission spectra in a large concentration range and temperature range.

a coumarin-based green light dye containing a triphenylamine ethylene side chain, the molecular structure of which is as described in the formula (I),

Wherein R1, R2 and R3 are independently represented by hydrogen, substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen.

Preferably, wherein R1, R2 and R3 are independently represented by hydrogen, substituted or unsubstituted C1-C4 alkyl or alkoxy.

Preferably, wherein R1 and R2 are independently represented by hydrogen, a C1-C4 alkoxy group, and R3 is independently represented by a substituted or unsubstituted C1-C4 alkyl group.

Preferably, R1 and R2 are the same.

Preferably, wherein R1 and R2 are preferably represented by hydrogen or methoxy, and R3 is independently represented by methyl.

The compound of the formula (I) is preferably a compound having the following structure:

The preparation method of the above green dye is prepared by the Heck coupling reaction using the formula A and the formula B:

The preparation method of the formula A is obtained by using C bromination in the following formula, and the reaction formula is as follows:

The preparation method of the formula B is prepared by reacting the following formula D with potassium vinyl fluoroborate under weak alkaline conditions, and the catalyst is tetrakistriphenylphosphine palladium, and the reaction formula is as follows:

The light conversion film is composed of the above green light dye and a cured polymer resin.

The cured polymer resin is an acrylate, an epoxy resin or a polyurethane.

The light conversion film has a total thickness of from 1 to 100 μm.

The use of the above green dye in a light conversion film.

The application is that the green light dye and the cured polymer resin are dissolved in toluene, then spin-coated into a film, dried and solidified to prepare an organic light conversion film, which is fixed on a backlight and applied to a flat display to realize Full color display.

The curing preparation method of the light conversion film may be heat curing or ultraviolet curing.

The backlight is a blue light source, and the cured polymer resin is a methyl methacrylate (PMMA) polymer resin.

The blue light source is a liquid crystal panel, an OLED or an inorganic LED light source.

The molecule represented by the formula (1) has a high fluorescence quantum yield and has a good application potential in the green light conversion film material. The material has strong luminescence, is insensitive to the preparation process, and has stable emission spectra in a large concentration range and temperature range.

DRAWINGS

Figure 1 is a schematic diagram of the synthetic route of the green dye GT1 of the present invention

2 is a schematic view showing a synthetic route of the green light dye GT2 of the present invention;

Figure 3 is an ultraviolet-visible absorption spectrum of the green light dye GT1 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state;

Figure 4 is a fluorescence emission spectrum of the green light dye GT1 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state,

Figure 5 is an ultraviolet-visible absorption spectrum of the green light dye GT2 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state;

Figure 6 is a fluorescence emission spectrum of the green dye GT2 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state.

Fig. 7 shows the fluorescence emission spectrum of the light conversion film formed by the classical green dye C545T mixed in PMMA at different ratios.

Fig. 8 is a fluorescence emission spectrum of a light conversion film prepared by the green dye GT2 of the present invention.

detailed description

In order to describe the present invention in more detail, the following examples are given, but are not limited thereto.

The dye molecules are all prepared by Heck coupling reaction:

Example 1 Synthesis of Green Light Dye GT1:

The synthetic route is shown in Figure 1.

(1) Synthesis of Compound 2a

Synthesis step: To a 250 mL reaction flask was added compound 1a (6.48 g, 20 mmol) (commercially available), potassium fluoroborate (3.22 g, 24 mmol), tetratriphenylphosphine palladium (8.3 g, 5%), K ₂ CO ₃ (6.48 g, 60 mmol), toluene (70 mL) and water (14 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 80 ° C by heating. The temperature was maintained for 8 hours, and the reaction of Compound 1a was completely confirmed by TLC.

After the reaction, the heating was stopped, the temperature was lowered to 20 ° C, and the reaction mixture was poured into water. EA (100 mL*3) was evaporated and evaporated. The crude column chromatography gave white compound 2a (4 g, yield 73.7%). ^{1 H NMR (d, J =} 10.88Hz, 1H) (400MHz, CHLOROFORM-d) ppm 5.15 5.63 (d, J = 17.61Hz, 1H) 6.66 (dd, J = 17.48,10.88Hz, 1H) 6.92-7.05 ( m, 4H) 7.09 (d, J = 8.19 Hz, 4H) 7.19 - 7.38 (m, 6H).

(2) Synthesis of Compound 4a

Synthesis step: Compound 3a (7 g, 30 mmol) (commercially available), NBS (5.9 g, 39 mmol) and chloroform (50 mL) were added to a 250 mL reaction flask. The reaction was carried out for 2 hours at room temperature, and the compound 3a was completely reacted by TLC.

Post-reaction treatment: The reaction was stopped, and the reaction mixture was poured into water, and dichloromethane (100 mL*2) was evaporated. The crude column chromatography gave pale yellow compound 4a (5 g, yield 53.7%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 1.21 (t, J = 7.09 Hz, 6H) 2.45 - 2.62 (m, 3H) 3.32-3.50 (m, 4H) 6.49 (d, J = 2.57 Hz, 1H) 6.60 (dd, J = 9.05, 2.57 Hz, 1H) 7.43 (d, J = 9.05 Hz, 1H).

(3) Synthesis of GT1

Synthesis step: Compound 4a (0.31 g, 1 mmol), compound 2a (0.352 g, 1.3 mmol) Pd ₂ (dba) ₃ (15 mg, 5%), tri-tert-butylphosphine (30 mg, 10%) was added to a 250 mL reaction flask. ), triethylamine (0.6 mL) and DMF (5 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 100 ° C by heating. The temperature was maintained for 12 hours, and the compound 4a was completely reacted by TLC.

After the reaction, the heating was stopped, and the mixture was cooled to 20 ° C. The reaction mixture was poured into water, ethyl acetate (50 mL*2) was evaporated and evaporated. The crude column chromatography gave the pale yellow compound GT1 (0.15 g, yield 30%).

¹ H NMR (400 MHz, CHLOROFORM-d) ppm 1.22 (t, J = 7.03 Hz, 7H) 2.50 (s, 3H) 3.42 (q, J = 7.05 Hz, 4H) 6.51 (s, 1H) 6.61 (d, J =9.17Hz,1H)6.97-7.07(m,6H)7.11(d,J=7.95Hz,4H)7.23(br.s.,2H)7.27(s,1H)7.40(d,J=8.31Hz,2H 7.47 (d, J = 8.93 Hz, 1H) 7.56 (d, J = 16.14 Hz, 1H).

Example 2 Synthesis of Green Light Dye GT2:

The synthetic route is shown in Figure 2.

(1) Synthesis of Compound 3b

Synthesis step: To a 250 mL reaction flask was added Compound 1b (4.58 g, 20 mmol) (commercially available), Compound 2b (commercially available) (8.5 g, 30 mmol), Pd ₂ (dba) ₃ (920 mg, 5%), Uncle Butylphosphine (400 mg, 10%), sodium tert-butoxide (4.58 g, 40 mmol) and toluene (100 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 110 ° C by heating. The temperature was maintained for 12 hours, and the reaction of Compound 1b was completely confirmed by TLC.

After the reaction, the heating was stopped, and the mixture was cooled to 20 ° C. The reaction mixture was poured into water, and ethyl acetate (10 mL*2) was evaporated. The crude product was purified by column chromatography to yieldd pale yellow compound 3b (4.3 g, yield 56.4%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 3.79 (s, 6H) 6.67-6.88 (m, 6H) 7.02 (d, J = 8.93 Hz, 4H) 7.23 (d, J = 8.80 Hz, 2H).

(2) Synthesis of Compound 4b

Synthesis step: To a 250 mL reaction flask was added compound 3b (4 g, 10.4 mmol), potassium fluoroborate (1.67 g, 12.5 mmol), tetratriphenylphosphine palladium (580 mg, 5%), K ₂ CO ₃ (3.24) g, 30 mmol), toluene (100 mL) and water (20 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 80 ° C by heating. The temperature was maintained for 8 hours, and the compound 3b was completely reacted by TLC. After the reaction, the heating was stopped, the temperature was lowered to 20 ° C, and the reaction mixture was poured into water. EA (100 mL*3) was evaporated and evaporated. The crude column chromatography gave white compound 4b (2.8 g, yield: 81.2%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 3.79 (s, 6H) 5.09 (d, J = 10.88 Hz, 1H) 5.58 (d, J = 17.61 Hz, 1H) 6.51-6.70 (m, 1H) 6.73 - 6.84 (m, 5H) 6.87 (d, J = 8.56 Hz, 1H) 6.95-7.09 (m, 4H) 7.14 - 7.25 (m, 2H).

(3) Synthesis of GT2

Synthesis step: To a 250 mL reaction flask was added compound 4b (1 g, 3.2 mmol) (commercially available), compound 4a (1.42 g, 4.2 mmol) Pd ₂ (dba) ₃ (50 mg, 5%), tri-tert-butylphosphine ( 200 mg, 10%), triethylamine (5 mL) and DMF (10 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 100 ° C by heating. The temperature was maintained for 12 hours, and the compound 4a was completely reacted by TLC. After the reaction, the heating was stopped, and the mixture was cooled to 20 ° C. The reaction mixture was poured into water, ethyl acetate (50 mL*2) was evaporated and evaporated. The crude column chromatography gave a pale yellow compound GT2 (0.55 g, yield 30.7%).

^{1 H NMR (400MHz, CHLOROFORM-} d) ppm 1.21 (t, J = 7.03Hz, 6H) 2.49 (s, 3H) 3.42 (q, J = 7.01Hz, 4H) 3.80 (s, 6H) 6.50 (d, J = 2.45 Hz, 1H) 6.61 (dd, J = 8.93, 2.32 Hz, 1H) 6.83 (d, J = 8.93 Hz, 4H) 6.90 (d, J = 8.56 Hz, 2H) 7.00 (d, J = 16.26 Hz, 1H) 7.06 (d, J = 8.93 Hz, 4H) 7.34 (d, J = 8.68 Hz, 2H) 7.46 (d, J = 9.05 Hz, 1H) 7.49 - 7.57 (m, 1H).

Example 3 Photophysical properties of green dyes GT1 and GT2:

The photophysical properties of the green dyes GT1 and GT2 in solution are determined by dissolving the corresponding dye in toluene or dichloromethane at a concentration of 1×10 ^-5 mol/L. The dye-based CCF film is the dye and corresponding The proportion of PMMA is dissolved in toluene, spin-coated and then dried. The photophysical properties of the dye film are determined by dissolving the dye in THF and spin-coating to prepare a film. CCF GT1 and GT2 film prepared (λ _max ≈450nm) have a good absorption of blue background, Figure 3, Figure 5, the light emitted by a green light, FIG. 4, FIG. GT1 and GT2 have strong luminescence (quantum yield EQE close to 70%), are not sensitive to the preparation process, and their emission spectra are stable over a large concentration and temperature range. Figure 7 is the fluorescence emission spectrum of the classic green dye C545T mixed in PMMA to form a light conversion film. It can be seen that small changes in the proportion of the impurities will cause a large change in the luminescence spectrum, and its luminescence stability. Very poor, Fig. 8 is the fluorescence emission light of the light conversion film prepared by the green dye GT2 of the present invention, and it can be seen that it is dispersed in PMMA at different concentrations, and its spectrum is very stable.

Claims

a coumarin-based green light dye containing a triphenylamine ethylene side chain having a molecular structure as described in the formula (I):

Wherein R1, R2 and R3 are independently represented by hydrogen, substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen.
The green dye according to claim 1, wherein R1, R2 and R3 are independently represented by hydrogen, a substituted or unsubstituted C1-C4 alkyl group, and a C1-C4 alkoxy group.
The green dye according to claim 2, wherein R1 and R2 are independently represented by hydrogen, a C1-C4 alkoxy group, and R3 is independently represented by a substituted or unsubstituted C1-C4 alkyl group.
The green dye according to claim 3, wherein R1 and R2 are the same.
The green dye according to claim 4, wherein R1 and R2 are represented by hydrogen, a C1-C4 alkoxy group, and R3 is independently represented by a C1-C4 alkyl group.
The green dye according to claim 5, having the following structural formula:
The method for preparing a green dye according to any one of claims 1 to 6, which is prepared by a Heck coupling reaction using the formula A and the formula B:
The method according to claim 7, wherein the preparation method of the formula A is obtained by using C bromination in the following formula, Should be as follows:
The method of claim 7 is prepared by reacting D with potassium vinyl fluoroborate in a weak basic condition under mild alkaline conditions, and the catalyst is tetrakistriphenylphosphine palladium. The reaction formula is as follows:
Use of the green light dye of any of claims 1-6 in a light converting film.