A reflective film and a preparation method and application thereof

Abstract

The application discloses a reflective film and a preparation method and application thereof, and belongs to the technical field of optical reflective films. The reflective film comprises a base film and a coating layer arranged on the surface of the base film; the coating layer contains a modified tetraazametallaporphyrin compound; the modified tetraazametallaporphyrin compound has a core-shell structure, the inner core is tetraazametallaporphyrin, and the outer shell is a zeolitic imidazolate framework; the chemical formula of the tetraazametallaporphyrin is: R1-R8 independently include: a hydrogen atom, a halogen element, a branched or cyclic aliphatic hydrocarbon group with 3-10 carbon atoms, an aromatic hydrocarbon group, a hydroxyl group, a sulfonic acid group or an amino group; M is a divalent metal ion; the zeolitic imidazolate framework contains Zn for coordination with N in the tetraazametallaporphyrin 2+ . The reflective film is resistant to light and has a wide color gamut. The reflective film can be further used in display devices.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of optical reflection film, in particular to a reflection film and a preparation method and application thereof. BACKGROUND

[0002] At present, as a light source of display lighting device, the commonly used scheme of white light emitting diode (WLED) includes combining a blue light LED with a yellow fluorescent powder for color adjustment, or mixing a blue light LED with green and red fluorescent powders for color adjustment. However, the above scheme will have the problem that the wide emission peak of the fluorescent powder will result in high yellow light intensity in the 590nm region of the modulated white light, affecting the color purity.

[0003] With the development of display technology, major manufacturers are increasingly pursuing the color reproduction capability of display devices. From the first generation sRGB to the current mainstream DCI P3, the color gamut is improving. The problem of insufficient color purity has always been an important factor restricting the improvement of the color gamut of the display.

[0004] Some existing technologies use quantum dots to improve the brightness and color gamut of the display, but these quantum dots often contain toxic heavy metals Cd or Pb, and the water and oxygen stability of the quantum dots is very poor, which requires high packaging technology and greatly increases the cost of the display device.

[0005] In view of this, the present application is proposed. SUMMARY

[0006] The purpose of the present application is to provide a reflection film and a preparation method and application thereof to solve or improve the above technical problems.

[0007] The present application can be realized as follows:

[0008] In a first aspect, the present application provides a reflection film, which comprises a base film and a coating layer arranged on the surface of the base film.

[0009] The coating layer contains a modified tetraazametallaporphyrin compound.

[0010] The modified tetraazametallaporphyrin compound has a core-shell structure, wherein the inner core is a tetraazametallaporphyrin, and the outer shell is a zeolitic imidazolate framework.

[0011] The chemical formula of the tetraazametallaporphyrin is: ; wherein R1-R8 independently includes: a hydrogen atom, a halogen element, a branched or cyclic aliphatic group with a carbon atom of 3-10, an aromatic hydrocarbon group, a hydroxyl group, a sulfonic acid group or an amino group; M is a divalent metal ion.

[0012] The zeolitic imidazolate framework contains Zn for coordination with N in the tetraazametallaporphyrin 2+ .

[0013] In optional embodiments, M comprises Cu 2+ , Zn 2+ , Co 2+ , Mg 2+ , Be 2+ , Pb 2+ , Sn 2+ , Ba 2+ , or Fe 2+ .

[0014] In optional embodiments, the method for preparing the modified tetraazametalloporphyrin compound comprises the following steps: mixing a tetraazametalloporphyrin colloidal solution with zinc acetate to form a pre-ligating complex; adding a 2-methylimidazole dispersion liquid dropwise to the pre-ligating complex for a ligating reaction to form a shell, and drying to obtain the modified tetraazametalloporphyrin compound.

[0015] In optional embodiments, the method for preparing the modified tetraazametalloporphyrin compound comprises at least one of the following features:

[0016] Feature 1: the molar ratio of Zn 2+ in the tetraazametalloporphyrin colloidal solution to zinc acetate is 1:18 to 1:22;

[0017] Feature 2: the 2-methylimidazole dispersion liquid comprises 2-methylimidazole and N,N-dimethylformamide at a mass ratio of 0.8:100 to 1.2:100;

[0018] Feature 3: the volume ratio of the 2-methylimidazole dispersion liquid to the pre-ligating complex is 1.8:1 to 2.2:1;

[0019] Feature 4: the dropping speed of the 2-methylimidazole dispersion liquid is 0.45 L / min to 0.55 L / min;

[0020] Feature 5: the dropping temperature is 20°C to 30°C, and the dropping time is 6h to 24h.

[0021] In optional embodiments, the preparation of the tetraazametalloporphyrin colloidal solution comprises dispersing tetraazametalloporphyrin in a solvent and ultrasonic treatment under ice bath conditions to form a colloid.

[0022] In optional embodiments, the mass ratio of the tetraazametalloporphyrin to the solvent is 2.5:1 to 3.5:1; optionally, the solvent comprises N,N-dimethylformamide (DMF).

[0023] In optional embodiments, the frequency of the ultrasonic treatment is 35kHz to 45kHz, and the time of the ultrasonic treatment is 25min to 35min.

[0024] In an optional embodiment, the preparation of the tetraazametallaporphyrin comprises: dissolving the phthalonitrile and the metal chloride in a mixed solvent, and refluxing under a protective atmosphere;

[0025] The metal chloride is a chloride of M in the chemical formula of the tetraazametallaporphyrin.

[0026] The molar ratio of the phthalonitrile to the metal chloride is 3.5:1 to 4.5:1.

[0027] The mixed solvent comprises 1,8-diazabicycloundec-7-ene and 1-pentanol in a volume ratio of 1:2.5 to 1:3.5.

[0028] The refluxing temperature is 155°C to 165°C, and the refluxing time is 4h to 8h.

[0029] In an optional embodiment, the coating further comprises an adhesive; optionally, the refractive index of the adhesive is 1.43 to 1.53; optionally, the adhesive comprises at least one of a thermosetting acrylic adhesive, a polyurethane resin, an epoxy resin, and a polyvinyl acetal resin.

[0030] In an optional embodiment, the coating further comprises organic coated particles; optionally, the particle size of the organic coated particles is 30μm to 60μm; optionally, the organic coated particles comprise at least one of PMMA particles, PBMA particles, PET particles, and PA particles.

[0031] In an optional embodiment, the coating further comprises an auxiliary agent; optionally, the auxiliary agent comprises at least one of a dispersant, a curing agent, and an antistatic agent; optionally, the dispersant comprises at least one of a polyurethane dispersant, a polyacrylate dispersant, a modified polyacrylate dispersant, and a polyester dispersant; optionally, the antistatic agent comprises at least one of a fatty alcohol phosphate antistatic agent, an alkyl phosphate antistatic agent, and a fatty alcohol polyoxyethylene ether antistatic agent; optionally, the curing agent comprises an isocyanate curing agent.

[0032] In a second aspect, the present application provides a method for preparing the reflective film according to the foregoing embodiments, comprising the following steps: preparing a coating on the surface of a base film.

[0033] In an optional embodiment, when the coating comprises the modified tetraazametallaporphyrin compound, the organic coated particles, the adhesive, and the auxiliary agent, the preparation of the coating comprises the following steps: mixing the adhesive, the organic coated particles, the auxiliary agent, and a fatty acid ester solvent to obtain a first coating liquid; adding a dispersion of the modified tetraazametallaporphyrin compound to the first coating liquid, and ultrasonicating to obtain a final coating liquid; coating the final coating liquid on the surface of the base film, and heat curing.

[0034] In an optional embodiment, the final coating solution contains 1 ppm to 20 ppm of the modified tetraazamacrocycle metalloporphyrin compound.

[0035] In an optional embodiment, the reflectivity of the base film is greater than 96%.

[0036] In an optional embodiment, the base film comprises at least one of foamed polyethylene terephthalate, polypropylene, and polycarbonate.

[0037] In an optional embodiment, the heat curing temperature is 115°C to 125°C, and the heat curing time is 1 minute to 3 minutes.

[0038] In an optional embodiment, the mass ratio of the adhesive, the organic coating particles, the additive, and the fatty acid ester solvent-like solvent is 8:1:0.5:6 to 12:1:1.5:10.

[0039] In an optional embodiment, the mass percentage of the modified tetraazamacrocycle metalloporphyrin compound in the modified tetraazamacrocycle metalloporphyrin compound dispersion is 0.05% to 0.2%.

[0040] In an optional embodiment, the mass ratio of the first coating solution to the modified tetraazamacrocycle metalloporphyrin compound dispersion is 1:1000 to 4:1000.

[0041] In an optional embodiment, the ultrasonic frequency is 35 kHz to 45 kHz, and the ultrasonic time is 15 minutes to 25 minutes.

[0042] In a third aspect, the present application provides a display device having the reflective film according to the foregoing embodiments.

[0043] The beneficial effects of the present application include:

[0044] The present application first proposes a reflective film containing a modified tetraazamacrocycle metalloporphyrin compound, which has a core-shell structure, wherein the inner core is a tetraazamacrocycle metalloporphyrin, and the outer shell is a zeolitic imidazolate framework; the chemical formula of the tetraazamacrocycle metalloporphyrin is: ; wherein R1 to R8 independently include a hydrogen atom, a halogen element, a branched or cyclic aliphatic group with 3 to 10 carbon atoms, an aromatic hydrocarbon group, a hydroxyl group, a sulfonic acid group, or an amino group; M is a divalent metal ion; the zeolitic imidazolate framework contains Zn 2+ .

[0045] The modified tetraazamacrocycle metalloporphyrin compound can absorb 580 nm to 640 nm stray light in a backlight source, thereby improving the color purity. The reflective film prepared by using the modified tetraazamacrocycle metalloporphyrin compound is resistant to light and has a wide color gamut. The reflective film can be further used in a display device. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0047] Figure 1 A schematic structural diagram of the reflective film provided by the present invention;

[0048] Figure 2 TEM image of the sample tested by transmission electron microscopy in Experimental Example 1;

[0049] Figure 3 The SEM image and EDS spectrum of CuTAP@ZIF-8 in Experimental Example 1;

[0050] Figure 4 This is the reflectivity curve of the reflective film prepared in Example 4 in Experimental Example 2.

[0051] Icons: 10-base film; 20-coating; 21-adhesive; 22-modified tetraazametalloporphyrin compound; 23-organic coated particles. DETAILED DESCRIPTION

[0052] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0053] The reflective film provided by the present invention and its preparation method and application are described in detail below.

[0054] The present invention provides a modified tetraazametalloporphyrin compound 22 (combined with Figure 1 ), the modified tetraazametalloporphyrin compound 22 has a core-shell structure, wherein the core is tetraazametalloporphyrin and the shell is a zeolite imidazole ester framework.

[0055] The chemical formula of tetraazametalloporphyrin is: Wherein, R1-R8 independently include: a hydrogen atom, a halogen element, a branched or cyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group, a hydroxyl group (-OH), a sulfonic acid group (-SH), or an amino group (-NH). The halogen element may illustratively include F, Cl, or Br.

[0056] M is a divalent metal ion, illustratively, M can include Cu 2+ , Zn 2+ , Co 2+ , Mg 2+ , Be 2+ , Pb 2+ , Sn 2+ , Ba 2+ , or Fe 2+ , etc.

[0057] Zn contained in the zeolitic imidazolate framework is used for coordination with N in the tetraazametallaporphyrin 2+ .

[0058] The modified tetraazametallaporphyrin compound 22 provided by the present application is denoted as MTAP@ZIF-8, wherein the inner core is denoted as MTAP (tetraazametallaporphyrin); and a zeolitic imidazolate framework capable of improving the light stability of the MTAP is grown on the surface layer of the inner core. The modified tetraazametallaporphyrin compound 22 can absorb 580 nm-640 nm miscellaneous color light in a backlight source, thereby improving the color purity thereof.

[0059] Correspondingly, the present application further provides a preparation method of the modified tetraazametallaporphyrin compound 22, which can include the following steps:

[0060] S1: mixing a tetraazametallaporphyrin colloidal solution with zinc acetate to form a pre-coordination complex.

[0061] In some optional embodiments, the molar ratio of Zn 2+ in the tetraazametallaporphyrin colloidal solution to zinc acetate can be 1:18 to 1:22, such as 1:18, 1:19, 1:20, 1:21 or 1:22, etc., and can also be other values within the range of 1:18 to 1:22. In some more typical embodiments, the molar ratio of Zn 2+ in the tetraazametallaporphyrin colloidal solution to zinc acetate is 1:20. The mixing time of the above-mentioned tetraazametallaporphyrin colloidal solution and zinc acetate can be 30 min. The zinc acetate is Zn(OAc)2.

[0062] In some optional embodiments, the preparation of the above-mentioned tetraazametallaporphyrin colloidal solution can include: dispersing tetraazametallaporphyrin in a solvent and ultrasonic treatment under ice bath conditions to form a colloid.

[0063] The mass ratio of the tetraazametallaporphyrin to the solvent can be 2.5:1 to 3.5:1, such as 2.5:1, 2.8:1, 3:1, 3.2:1 or 3.5:1, etc., and can also be other values within the range of 2.5:1 to 3.5:1. Illustratively, the solvent can include N,N-dimethylformamide (DMF).

[0064] The frequency of the ultrasonic treatment can be 35 kHz to 45 kHz, such as 35 kHz, 38 kHz, 40 kHz, 42 kHz, or 45 kHz, or other values within the range of 35 kHz to 45 kHz. The time of the ultrasonic treatment can be 25 min to 35 min, such as 25 min, 28 min, 30 min, 32 min, or 35 min, or other values within the range of 25 min to 35 min.

[0065] By ultrasonic treatment under the above ice bath condition, a uniform colloid is obtained, and then the undispersed particles are filtered out by a filter membrane (pore size of 0.22 μm) to obtain a uniformly dispersed MTAP colloidal solution.

[0066] In some alternative embodiments, the preparation of the above tetraazametalloporphyrin (MTAP) can include: dissolving phthalonitrile and a metal chloride in a mixed solvent, and refluxing under a protective atmosphere (such as a nitrogen atmosphere, etc.).

[0067] The metal chloride is a chloride of the element M in the chemical formula of the tetraazametalloporphyrin.

[0068] The molar ratio of phthalonitrile to the metal chloride can be 3.5:1 to 4.5:1, such as 3.5:1, 3.8:1, 4:1, 4.2:1, or 4.5:1, or other values within the range of 3.5:1 to 4.5:1. In some more typical embodiments, the molar ratio of phthalonitrile to the metal chloride is 4:1.

[0069] The mixed solvent can include 1,8-diazabicycloundec-7-ene (DBU) and 1-pentanol in a volume ratio of 1:2.5 to 1:3.5 (such as 1:2.5, 1:2.8, 1:3, 1:3.2, or 1:3.5, or other values within the range of 1:2.5 to 1:3.5). In some more typical embodiments, the mixed solvent is obtained by mixing DBU and 1-pentanol in a volume ratio of 1:3.

[0070] In some alternative embodiments, the refluxing temperature can be 155°C to 165°C, such as 155°C, 158°C, 160°C, 162°C, or 165°C, or other values within the range of 155°C to 165°C.

[0071] The refluxing time can be 4 h to 8 h, such as 4 h, 5 h, 6 h, 7 h, or 8 h, or other values within the range of 4 h to 8 h.

[0072] Further, the crude product obtained by refluxing is rapidly cooled by ice bath, and then centrifuged, and the precipitate is sequentially washed with ethanol and deionized water, and vacuum dried to obtain the tetraazametalloporphyrin.

[0073] S2: drop 2-methylimidazole dispersion liquid into the pre-ligating complex to perform a ligating reaction to form a shell, dry to obtain a modified tetraazametallaporphyrin compound 22.

[0074] In some alternative embodiments, the 2-methylimidazole dispersion liquid (2-MIM) can include 2-methylimidazole and N,N-dimethylformamide in a mass ratio of 0.8:100 to 1.2:100. The mass ratio of 2-methylimidazole and N,N-dimethylformamide can be 0.8:100, 0.9:100, 1:100, 1.1:100, or 1.2:100, etc., or other values within the range of 0.8:100 to 1.2:100. In some more typical embodiments, the 2-methylimidazole dispersion liquid (2-MIM) includes 2-methylimidazole and N,N-dimethylformamide in a mass ratio of 1:100.

[0075] The above dropwise addition process is carried out under a protective atmosphere, which can be an argon atmosphere.

[0076] In some alternative embodiments, the volume ratio of the 2-methylimidazole dispersion liquid to the pre-ligating complex can be 1.8:1 to 2.2:1, such as 1.8:1, 1.9:1, 2:1, 2.1:1, or 2.2:1, etc., or other values within the range of 1.8:1 to 2.2:1. In some more typical embodiments, the volume ratio of the 2-methylimidazole dispersion liquid to the pre-ligating complex is 2:1.

[0077] In some alternative embodiments, the dropwise addition speed of the 2-methylimidazole dispersion liquid can be 0.45L / min~0.55L / min, such as 0.45L / min, 0.48L / min, 0.5L / min, 0.52L / min, or 0.55L / min, etc., or other values within the range of 0.45L / min~0.55L / min.

[0078] If the dropwise addition speed of the 2-methylimidazole dispersion liquid is less than 0.45L / min, it is easy to cause local concentration imbalance of the reaction system, leading to free crystal nucleus proliferation, loose shell, and even core-shell separation, etc. defects; if the dropwise addition speed of the 2-methylimidazole dispersion liquid is greater than 0.55L / min, it is easy to cause insufficient reaction and uneven shell.

[0079] In some alternative embodiments, the dropwise addition temperature can be 20℃~30℃, such as 20℃, 22℃, 25℃, 28℃, or 30℃, etc., or other values within the range of 20℃~30℃. The dropwise addition time can be 6h~24h, such as 6h, 10h, 14h, 18h, 22h, or 24h, etc., or other values within the range of 6h~24h.

[0080] If the dropping time is shorter than 6 hours, the shell layer will be too thin and the core will not be fully coated. If the dropping time is longer than 24 hours, the shell layer will be too thick, the crystal size will be too large, and the light emitting performance will be affected.

[0081] After the dropping is completed, liquid nitrogen is added for quenching to terminate the reaction.

[0082] Further, the preparation of the reflective film can also include a post-treatment process, which can also be understood as a purification process.

[0083] In some optional embodiments, the purification process can include: centrifuging the MTAP@ZIF-8 reaction solution obtained by the S2 reaction (the centrifugal speed can be, for example, 8000 rpm, and the centrifugal time can be, for example, 15 min), washing the precipitate (the washing liquid used for washing can be, for example, methanol, and the number of washing times can be, for example, 3 times), soaking in methanol after washing to completely remove DMF (the soaking time can be, for example, 24 h), and then drying (the drying temperature can be, for example, 120°C).

[0084] As described above, by in-situ synthesis, the ZIF-8 shell layer (Zn 2+ which is combined with the N atoms in the MTAP) is grown on the surface of the MTAP with a molecular skeleton of a macrocyclic organic molecular structure, which can inhibit the photobleaching phenomenon and improve the light stability, thereby facilitating the stable operation of the reflective film under long-time light working conditions.

[0085] In addition, the present application also provides a reflective film, as shown in the figure, which comprises a base film 10 and a coating layer 20 arranged on the surface of the base film 10. The coating layer 20 contains a modified tetraazametallaporphyrin compound 22, organic coating particles 23 and an adhesive 21. Figure 1

[0086] In some optional embodiments, the base film 10 is a white reflective base film 10 with a reflectivity of >96%. The base film 10 can exemplarily include at least one of foamed polyethylene terephthalate (PET), polypropylene (PP) and polycarbonate (PC).

[0087] The coating layer 20 contains the modified tetraazametallaporphyrin compound 22 described above.

[0088] In some optional embodiments, the coating layer 20 also contains the adhesive 21. The refractive index of the adhesive 21 can be 1.43-1.53, such as 1.43, 1.45, 1.47, 1.5 or 1.53, etc., or other values within the range of 1.43-1.53. As an enumeration, the adhesive 21 described above can exemplarily but non-limitingly include at least one of thermosetting acrylic glue, polyurethane resin, epoxy resin and polyvinyl acetal resin, etc. ​

[0089] In some optional embodiments, the coating layer 20 further contains organic coated particles 23. The particle size of the organic coated particles 23 can be 30 μm to 60 μm, such as 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm or 60 μm, or other values within the range of 30 μm to 60 μm.

[0090] If the particle size of the organic coated particles 23 is less than 30 μm, the organic coated particles cannot sufficiently support the upper LGP of the reflective film, which can easily cause scratches on the LGP. If the particle size of the organic coated particles 23 is greater than 60 μm, the thickness of the backlight module will be increased, which is not in line with the development trend of thin display.

[0091] By way of illustration, the organic coated particles 23 can exemplarily but non-limitatively include at least one of PMMA particles, PBMA particles, PET particles and PA particles.

[0092] In some optional embodiments, the coating layer 20 further contains an auxiliary agent.

[0093] The auxiliary agent can include at least one of a dispersing agent, a curing agent and an antistatic agent. The dispersing agent can exemplarily but non-limitatively include at least one of a polyurethane dispersing agent, a polyacrylate dispersing agent, a modified polyacrylate dispersing agent and a polyester dispersing agent. The antistatic agent can exemplarily but non-limitatively include at least one of a fatty alcohol phosphate antistatic agent, an alkyl phosphate antistatic agent and a fatty alcohol polyoxyethylene ether antistatic agent. The curing agent can exemplarily but non-limitatively include an isocyanate curing agent.

[0094] As described above, the organic coated particles 23 contained in the reflective film can improve the scratching and adsorption problems of the reflective film and the light guide plate. The modified tetraazametalloporphyrin compound 22 contained in the reflective film can absorb the 580 nm to 640 nm stray light in the backlight source, thereby improving the color purity.

[0095] Correspondingly, the present application further provides a preparation method of the reflective film, which comprises the following steps: preparing the coating layer 20 on the surface of the base film 10.

[0096] When the coating layer 20 contains the modified tetraazametalloporphyrin compound 22, the organic coated particles 23, the adhesive 21 and the auxiliary agent, the preparation of the coating layer 20 can comprise the following steps: mixing the adhesive 21, the organic coated particles 23, the auxiliary agent and the fatty acid ester solvent to obtain a first coating liquid; adding a dispersion liquid of the modified tetraazametalloporphyrin compound 22 to the first coating liquid, and ultrasonicating to obtain a final coating liquid; coating the final coating liquid on the surface of the base film 10, and heat curing.

[0097] In some alternative embodiments, the mass ratio of the adhesive 21, the organic coated particles 23, the auxiliary agent, and the fatty acid ester solvent-like solvent can be 8:1:0.5:6 to 12:1:1.5:10. In some typical embodiments, the mass ratio of the adhesive 21, the organic coated particles 23, the auxiliary agent, and the fatty acid ester solvent-like solvent can be 10:1:1:8. The fatty acid ester solvent-like solvent described above can include at least one of ethyl acetate and butyl acetate, and exemplarily, the fatty acid ester solvent-like solvent can include ethyl acetate and butyl acetate in a mass ratio of 1:1.

[0098] In some alternative embodiments, the mass percentage of the modified tetraazametallaporphyrin compound 22 in the modified tetraazametallaporphyrin compound 22 dispersion liquid can be 0.05% to 0.2%, such as 0.05%, 0.1%, 0.15%, or 0.2%, or other values within the range of 0.05% to 0.2%.

[0099] In some alternative embodiments, the mass ratio of the first coating liquid and the dispersion liquid of the modified tetraazametallaporphyrin compound 22 can be 1:1000 to 4:1000, such as 1:1000, 1.5:1000, 2:1000, 2.5:1000, 3:1000, 3.5:1000, or 4:1000, or other values within the range of 1:1000 to 4:1000.

[0100] If the mass ratio of the first coating liquid and the dispersion liquid of the modified tetraazametallaporphyrin compound 22 is less than 1:1000 (such as 1:1000), it is not conducive to the color gamut improvement of the reflective film; if the mass ratio of the first coating liquid and the dispersion liquid of the modified tetraazametallaporphyrin compound 22 is greater than 4:1000 (such as 5:1000), it will affect the backlight brightness.

[0101] In some alternative embodiments, the final coating liquid contains 1 ppm to 20 ppm of the modified tetraazametallaporphyrin compound; if the amount of the modified tetraazametallaporphyrin compound 22 contained in the final coating liquid is less than 1 ppm, it is not conducive to its absorption of stray light in the 580 nm to 640 nm wave band, resulting in insignificant color gamut improvement effect; if the amount of the modified tetraazametallaporphyrin compound 22 contained in the final coating liquid is higher than 20 ppm, the reflective film absorbs too much backlight, resulting in reduced display brightness. Further, the final coating liquid can contain 1 ppm to 5 ppm of the modified tetraazametallaporphyrin compound.

[0102] In addition, if the content of the organic coated particles 23 in the final coating liquid is too low, the air barrier layer cannot be completely formed between the reflective film and the light guide plate (LGP) thereon, and the light guide plate is easily scratched; if the content of the organic coated particles 23 in the final coating liquid is too high, the gloss of the reflective film is too low, reducing the backlight brightness.

[0103] In some optional embodiments, the ultrasonic frequency can be 35 kHz-45 kHz, such as 35 kHz, 38 kHz, 40 kHz, 42 kHz, or 45 kHz, etc., or other values within the range of 35 kHz-45 kHz. The ultrasonic time can be 15 min-25 min, such as 15 min, 18 min, 20 min, 22 min, or 25 min, etc., or other values within the range of 15 min-25 min.

[0104] In some optional embodiments, the temperature of the thermal curing can be 115℃-125℃, such as 115℃, 118℃, 120℃, 122℃, or 125℃, etc., or other values within the range of 115℃-125℃.

[0105] The thermal curing time can be 1 min-3 min, such as 1 min, 1.5 min, 2 min, 2.5 min, or 3 min, etc., or other values within the range of 1 min-3 min.

[0106] In addition, the present application also provides a display device having the above-mentioned reflective film.

[0107] As for the reflective film provided by the present application, the yellow light at 590 nm can be effectively absorbed by the reflective film, that is, the reflective film provided by the present application can improve the color purity of the light source and increase the color gamut of the display device.

[0108] The features and performances of the present application are further described in detail below in combination with embodiments.

[0109] Example 1

[0110] The present embodiment provides a modified tetraazametallaporphyrin compound 22, and the preparation method thereof comprises:

[0111] S1: mixing the tetraazametallaporphyrin colloidal solution with zinc acetate to form a pre-ligating complex.

[0112] S11: preparing tetraazametallaporphyrin.

[0113] Take 4 mmol of phthalonitrile and 1 mmol of CuCl2 and dissolve them in 20 mL of mixed solvent (the mixed solvent is composed of 5 mL of DBU and 15 mL of 1-pentanol), under the protection of nitrogen, reflux at 160℃ for 6 h to obtain CuTAP crude product. The CuTAP crude product is quickly cooled in an ice bath, then centrifuged, and the precipitate is sequentially washed with 40 mL of ethanol and 40 mL of deionized water, and vacuum dried to obtain tetraazametallaporphyrin (CuTAP).

[0114] S12: preparing a tetraazametallaporphyrin colloidal solution.

[0115] 15 mg CuTAP was dispersed in 5 mL anhydrous DMF, and was treated in an ice bath for 30 min in a 40 kHz ultrasonic instrument to form a uniform colloid, and then un-dispersed particles were filtered out through a 0.22 μm filter membrane to obtain a uniformly dispersed CuTAP colloid solution.

[0116] S13: Preparation of a pre-ligating complex.

[0117] 60 mg Zn(OAc)2 was added to the above CuTAP colloid solution, and was stirred for 30 min to form a pre-ligating complex. The molar ratio of CuTAP to Zn in Zn(OAc)2 was 1:20. 2+

[0118] S2: 2-Methylimidazole dispersion was added dropwise to the pre-ligating complex to perform a ligating reaction to form the shell, and was dried to obtain a modified tetraazametallaporphyrin compound 22.

[0119] Specifically, 0.1 g of 2-methylimidazole (2-MIM) was dissolved in 10 g of anhydrous DMF to obtain a 2-MIM dispersion. The 2-MIM dispersion was added dropwise to the pre-ligating complex at a speed of 0.5 L / min (the volume ratio of the 2-MIM dispersion to the pre-ligating complex was 2:1) under an argon atmosphere at 25°C, and the reaction was terminated after 6 h by adding liquid nitrogen to obtain a CuTAP@ZIF-8 reaction solution.

[0120] S3: Post-treatment.

[0121] The CuTAP@ZIF-8 reaction solution obtained in step S2 was centrifuged at 8000 rpm for 15 min, and the precipitate was washed with 10 mL of methanol for 3 times each time, and then was soaked in methanol for 24 h to completely remove DMF, and then was vacuum dried at 12°C to obtain a modified tetraazametallaporphyrin compound 22 (CuTAP@ZIF-8).

[0122] Example 2

[0123] The present example provides a modified tetraazametallaporphyrin compound 22, and a preparation method thereof includes:

[0124] S1: A tetraazametallaporphyrin colloid solution was mixed with zinc acetate to form a pre-ligating complex.

[0125] S11: Preparation of a tetraazametallaporphyrin.

[0126] ​Take 3.5 mmol of phthalonitrile and 1 mmol of CuCl2 and dissolve them in 20 mL of mixed solvent (the mixed solvent is composed of 5 mL of DBU and 12.5 mL of 1-pentanol), under the protection of nitrogen, reflux at 155°C for 8 h to obtain the CuTAP crude product. The CuTAP crude product is rapidly cooled in an ice bath, then centrifuged, and the precipitate is washed with 40 mL of ethanol and 40 mL of deionized water in turn, and vacuum dried to obtain the tetraazametallaporphyrin (CuTAP).

[0127] S12: Preparation of a tetraazametallaporphyrin colloidal solution.

[0128] Disperse 12.5 mg of CuTAP in 5 mL of anhydrous DMF, and place it in an ice bath and treat it with a 35 kHz ultrasonic instrument for 35 min to form a uniform colloid, then filter out the undispersed particles through a 0.22 μm filter membrane to obtain a uniformly dispersed CuTAP colloidal solution.

[0129] S13: Preparation of a pre-ligating complex.

[0130] Add Zn(OAc)2 to the above CuTAP colloidal solution to make the molar ratio of CuTAP to Zn 2+ in Zn(OAc)2 1:18, stir for 30 min to form a pre-ligating complex. The molar ratio of MTAP to Zn 2+ in Zn(OAc)2 is 1:20.

[0131] S2: Add a 2-methylimidazole dispersion to the pre-ligating complex to perform a ligating reaction to form the shell, and dry to obtain a modified tetraazametallaporphyrin compound 22.

[0132] Specifically, 80 mg of 2-methylimidazole (2-MIM) is dissolved in 10000 mg of anhydrous DMF to obtain a 2-MIM dispersion. Under an argon atmosphere at 25°C, the 2-MIM dispersion is added to the pre-ligating complex at a rate of 0.45 L / min (the volume ratio of the 2-MIM dispersion to the pre-ligating complex is 1.8:1), and after 24 h of reaction, liquid nitrogen is added to quench the reaction to obtain a CuTAP@ZIF-8 reaction solution.

[0133] S3: Post-treatment.

[0134] The CuTAP@ZIF-8 reaction solution obtained in step S2 is centrifuged at 8000 rpm for 15 min, the precipitate is washed with 10 mL of methanol three times each time, then soaked in methanol for 24 h to completely remove the DMF, and then vacuum dried at 12°C to obtain a modified tetraazametallaporphyrin compound 22 (CuTAP@ZIF-8).

[0135] Example 3

[0136] The embodiment provides a modified tetraazamacrocycle metalloporphyrin compound 22, and a preparation method thereof.

[0137] S1: mixing a tetraazamacrocycle metalloporphyrin colloidal solution with zinc acetate to form a pre-ligating complex.

[0138] S11: preparing a tetraazamacrocycle metalloporphyrin.

[0139] 4.5 mmol of phthalonitrile and 1 mmol of CuCl2 are dissolved in 20 mL of a mixed solvent (the mixed solvent is composed of 5 mL of DBU and 17.5 mL of 1-pentanol), and then, under the protection of nitrogen, the mixture is refluxed at 165 DEG C for 6 h to obtain a CuTAP crude product. The CuTAP crude product is rapidly cooled in an ice bath, and then, centrifuged, and the precipitate is sequentially washed with 40 mL of ethanol and 40 mL of deionized water, and then, dried in vacuum to obtain a tetraazamacrocycle metalloporphyrin (CuTAP).

[0140] S12: preparing a tetraazamacrocycle metalloporphyrin colloidal solution.

[0141] 17.5 mg of CuTAP is dispersed in 5 mL of anhydrous DMF, and then, placed in a 45 kHz ultrasonic instrument under the condition of an ice bath to be treated for 25 min to form a uniform colloidal solution, and then, un-dispersed particles are filtered out through a 0.22 mu m filter membrane to obtain a uniformly dispersed CuTAP colloidal solution.

[0142] S13: preparing a pre-ligating complex.

[0143] Zn(OAc)2 is added to the CuTAP colloidal solution to make the molar ratio of CuTAP to Zn in Zn(OAc)2 be 1:22, and then, stirred for 30 min to form a pre-ligating complex. 2+

[0144] S2: adding a 2-methylimidazole dispersion to the pre-ligating complex to perform a ligating reaction to form the shell, and then, drying to obtain the modified tetraazamacrocycle metalloporphyrin compound 22.

[0145] Specifically, 120 mg of 2-methylimidazole (2-MIM) is dissolved in 10000 mg of anhydrous DMF to obtain a 2-MIM dispersion. Under the condition of a constant temperature of 25 DEG C and an argon atmosphere, the 2-MIM dispersion is added to the pre-ligating complex at a speed of 0.55 L / min (the volume ratio of the 2-MIM dispersion to the pre-ligating complex is 2.2:1), and then, after reaction for 12 h, liquid nitrogen is added to quench the reaction to obtain a CuTAP@ZIF-8 reaction liquid.

[0146] S3: post-treatment.

[0147] ​The CuTAP@ZIF-8 reaction solution obtained in step S2 was centrifuged at 8000 rpm for 15 min, the precipitate was washed with 10 mL of methanol for 3 times each time, then was immersed in methanol for 24 h to completely remove DMF, and then was dried under vacuum at 12℃ to obtain the modified tetraazaporphyrin compound 22 (CuTAP@ZIF-8).

[0148] Example 4

[0149] The present embodiment provides a reflective film, and a preparation method thereof, which comprises the following steps:

[0150] Step (1): Preparation of a first coating liquid.

[0151] 16 g of an adhesive (polyurethane resin), 2 g of PET organic coating particles 23 (with a particle size of 45 μm), 1 g of an additive (a modified polyacrylate dispersant, a fatty alcohol polyoxyethylene ether antistatic agent and an isocyanate curing agent with a mass ratio of about 1:5:45), 6 g of ethyl acetate and 6 g of butyl acetate were uniformly mixed to obtain a first coating liquid.

[0152] Step (2): Preparation of a final coating liquid.

[0153] 0.12 mg of CuTAP@ZIF-8 powder prepared in Example 1 was dispersed in ethyl acetate to obtain a CuTAP@ZIF-8 dispersion liquid with a mass fraction of 0.1 wt%. The CuTAP@ZIF-8 dispersion liquid was added to the first coating liquid (the mass ratio of the first coating liquid to the CuTAP@ZIF-8 dispersion liquid was 1:1000), and then was treated in a 40 kHz ultrasonic instrument for 20 min to obtain a final coating liquid with a CuTAP@ZIF-8 concentration of 1 ppm.

[0154] Step (3): Coating and drying.

[0155] The final coating liquid was uniformly coated on the surface of a white reflective base film 10 (the base film 10 was specifically a base film 10 with a thickness of 225 μm produced by Ningbo Changyang Science and Technology Co., Ltd., China, with a model number of FDX225, and a reflectivity of about 97%) by using an OSP-80 wire bar, and the wet film thickness was 80 μm. Then, the coated film was heat cured at 120℃ for 2 min to obtain a reflective film with a coating layer 20.

[0156] Example 5

[0157] The present embodiment provides a reflective film, and a preparation method thereof, which comprises the following steps:

[0158] Step (1): Preparation of a first coating liquid.

[0159] Take 24 g of adhesive (epoxy resin), 2 g of PET organic coated particles 23 (particle size 30 μm), 3 g of additives (mass ratio of polyurethane dispersant, fatty alcohol phosphate antistatic agent and isocyanate curing agent is about 1:6:40), 10 g of ethyl acetate and 10 g of butyl acetate, and mix them uniformly to obtain a first coating liquid.

[0160] Step (2): Preparation of the final coating liquid.

[0161] Take 0.12 mg of CuTAP@ZIF-8 powder prepared in Example 2 and disperse it in ethyl acetate to obtain a CuTAP@ZIF-8 dispersion with a mass fraction of 0.05 wt%. Add the CuTAP@ZIF-8 dispersion to the first coating liquid (mass ratio of the first coating liquid to the CuTAP@ZIF-8 dispersion is 2:1000), and then treat it in a 35 kHz ultrasonic instrument for 25 min to obtain a final coating liquid with a CuTAP@ZIF-8 concentration of 1 ppm.

[0162] Step (3): Coating and drying.

[0163] Coat the final coating liquid on the surface of the white reflective base film 10 (the base film 10 is specifically a base film 10 with a thickness of 225 μm produced by Ningbo Changyang Technology Co., Ltd. in China, and the model number is FDX225, and the reflectivity is about 97%) with an OSP-80 wire bar, and the wet film thickness is 80 μm, and then heat cure it at 115°C for 3 min to obtain a reflective film with a coating layer 20.

[0164] Example 6

[0165] The present embodiment provides a reflective film, and the preparation method thereof comprises:

[0166] Step (1): Preparation of the first coating liquid.

[0167] Take 24 g of adhesive (epoxy resin), 2 g of PET organic coated particles 23 (particle size 30 μm), 3 g of additives (mass ratio of polyurethane dispersant, fatty alcohol phosphate antistatic agent and isocyanate curing agent is about 1:6:40), 10 g of ethyl acetate and 10 g of butyl acetate, and mix them uniformly to obtain a first coating liquid.

[0168] Step (2): Preparation of the final coating liquid.

[0169] 0.12 mg of CuTAP@ZIF-8 powder prepared in Example 3 was weighed and dispersed in ethyl acetate to obtain a CuTAP@ZIF-8 dispersion with a mass fraction of 0.2 wt%. The first coating solution was added with the CuTAP@ZIF-8 dispersion (the mass ratio of the first coating solution to the CuTAP@ZIF-8 dispersion was 1:1000), followed by treatment in a 45 kHz ultrasonic instrument for 15 min to obtain a final coating solution with a CuTAP@ZIF-8 concentration of 1 ppm.

[0170] Step (3): coating and drying.

[0171] The final coating solution was uniformly coated on the surface of a white reflective base film 10 (the base film 10 was specifically a base film 10 with a thickness of 225 μm produced by Ningbo Grand Solar Technology Co., Ltd. in China, with a model number of FDX225, and a reflectivity of about 97%) using an OSP-80 wire bar, and the wet film thickness was 80 μm. Then, the film was heat cured at 125 °C for 1 min to obtain a reflective film with a coating layer 20.

[0172] Example 7

[0173] The difference between this example and Example 4 is that the concentration of CuTAP@ZIF-8 in the final coating solution is 3 ppm.

[0174] Example 8

[0175] The difference between this example and Example 4 is that the concentration of CuTAP@ZIF-8 in the final coating solution is 5 ppm.

[0176] Example 9

[0177] The difference between this example and Example 4 is that the concentration of CuTAP@ZIF-8 in the final coating solution is 10 ppm.

[0178] Example 10

[0179] The difference between this example and Example 4 is that the concentration of CuTAP@ZIF-8 in the final coating solution is 20 ppm.

[0180] Comparative Example 1

[0181] The difference between this comparative example and Example 4 is that the first coating solution was directly coated on the surface of the base film 10. That is, the coating layer 20 does not contain CuTAP@ZIF-8.

[0182] Comparative Example 2

[0183] The difference between this comparative example and Example 4 is that the CuTAP@ZIF-8 powder was replaced with an equal amount of CuTAP powder that was not coated with ZIF-8.

[0184] Comparative Example 3

[0185] The present comparative example differs from Example 7 in that the CuTAP@ZIF-8 powder is replaced with an equivalent amount of CuTAP powder that is not coated with ZIF-8.

[0186] Comparative Example 4

[0187] The present comparative example differs from Example 8 in that the CuTAP@ZIF-8 powder is replaced with an equivalent amount of CuTAP powder that is not coated with ZIF-8.

[0188] Comparative Example 5

[0189] The present comparative example differs from Example 9 in that the CuTAP@ZIF-8 powder is replaced with an equivalent amount of CuTAP powder that is not coated with ZIF-8.

[0190] Comparative Example 6

[0191] The present comparative example differs from Example 10 in that the CuTAP@ZIF-8 powder is replaced with an equivalent amount of CuTAP powder that is not coated with ZIF-8.

[0192] Comparative Example 7

[0193] The present comparative example differs from Example 4 in that the concentration of CuTAP@ZIF-8 in the final coating solution is 0.3 ppm.

[0194] Comparative Example 8

[0195] The present comparative example differs from Example 4 in that the dropwise addition rate of the 2-methylimidazole dispersion solution is 0.3 L / min.

[0196] Comparative Example 9

[0197] The present comparative example differs from Example 4 in that the dropwise addition rate of the 2-methylimidazole dispersion solution is 0.8 L / min.

[0198] Comparative Example 10

[0199] The present comparative example differs from Example 4 in that the concentration of CuTAP@ZIF-8 in the final coating solution is 30 ppm.

[0200] Comparative Example 11

[0201] The present comparative example differs from Example 4 in that the concentration of CuTAP@ZIF-8 in the final coating solution is 50 ppm.

[0202] Test Example 1

[0203] The CuTAP@ZIF-8 prepared in Example 1 was dispersed in toluene to prepare a transmission electron microscope (TEM) test sample. The TEM image is shown in FIG. Figure 2 shown.

[0204] Depend on Figure 2 It can be seen that the CuTAP@ZIF-8 crystal has an obvious core-shell structure, indicating that the ZIF-8 shell has been successfully grown on the CuTAP surface.

[0205] In addition, the CuTAP@ZIF-8 prepared in Example 1 was observed by scanning electron microscopy and energy spectrum detection. Figure 3 As shown in (a), the EDS spectrum is as follows Figure 3 As shown in (b) and (c), Figure 3 (b) and (c) are the energy spectrum results of Cu and Zn corresponding to the dotted box in (a). Figure 3 It can be seen that Cu and Zn elements can be detected in the above samples, further confirming the successful growth of the ZIF-8 shell.

[0206] Test Example 2

[0207] The reflectivity test of the reflective film prepared in Example 4 was conducted: the reflectivity of the coated reflective film sample was tested in the range of 360nm to 740nm using the UltraScan VIS spectrophotometer from HunterLab. The reflectivity curve is shown in the results. Figure 4 As shown by Figure 4 It can be seen that there is an obvious depression at 590 nm, which is due to the absorption of yellow-orange light at this wavelength by CuTAP@ZIF-8 in the reflective film coating 20 .

[0208] Test Example 3

[0209] The reflective films prepared in Examples 4 to 10 and Comparative Examples 1 to 11 were subjected to performance tests in the following manner.

[0210] Luminance and color coordinate test: Assemble the reflective films into a backlight in the following order from bottom to top: KSF lamp → reflective film → light guide plate → diffuser → prism sheet (90°) → prism sheet (0°) → diffuser. Use a BM-7A luminance meter from TOPCON to perform luminance and color coordinate tests.

[0211] The reflectivity test is the same as that in Test Example 2.

[0212] The test results are shown in Table 1.

[0213] Table 1 Test results

[0214]

[0215] As can be seen from Table 1, as the adding concentration of the tetraazametallaporphyrin compound increases, the color gamut improvement effect also increases. However, a large amount of tetraazametallaporphyrin compound addition also causes a large loss of luminance, so it is necessary to balance the contradiction between color gamut improvement and luminance loss in sample preparation.

[0216] In addition, it can be seen from the data in the table that under 800H light, the reflectivity of the sample added with CuTAP at 590nm has a significant rebound and tends to approach Comparative Example 1 without CuTAP, indicating that CuTAP in the coating 20 decomposes under light. The reflectivity of the sample added with CuTAP@ZIF-8 before and after light is almost unchanged, indicating that the ZIF-8 shell coating has a significant effect on improving the light stability of CuTAP.

[0217] The reflectivity at 590nm of the samples in Comparative Example 8 and Comparative Example 9 before and after light appears a rebound as in Comparative Examples 2-6, but the luminance loss is serious, indicating that too fast or too slow dropping speed in the reaction process has a bad effect on the growth of the shell.

[0218] In summary, the modified tetraazametallaporphyrin compound 22 provided by the present application can absorb 580nm-640nm stray light in the backlight source and improve its color purity. By preparing a reflective film from the modified tetraazametallaporphyrin compound 22, the reflective film can be resistant to light and have a wide color gamut. The reflective film can be further used in display devices.

[0219] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A reflective film, characterized in that: The reflective film includes a base film and a coating layer arranged on the surface of the base film; The coating contains a modified tetraazametalloporphyrin compound; The modified tetraazametalloporphyrin compound has a core-shell structure, wherein the core is tetraazametalloporphyrin and the shell is a zeolite imidazolate framework; The chemical formula of the tetraazametalloporphyrin is: Wherein, R1~R8 independently include: hydrogen atom, halogen element, branched or cyclic aliphatic hydrocarbon group with 3 to 10 carbon atoms, aromatic hydrocarbon group, hydroxyl group, sulfonic acid group or amino group; M is Cu 2+ ; The zeolite imidazolate framework contains Zn for coordinating with N in the tetraazametalloporphyrin. 2+ ; The final coating liquid for forming the coating layer contains 1ppm to 20ppm of the modified tetraazametalloporphyrin compound.

2. The reflective film according to claim 1, wherein The preparation method of the modified tetraazametalloporphyrin compound comprises the following steps: mixing a tetraazametalloporphyrin colloidal solution with zinc acetate to form a pre-coordination complex; dropping a 2-methylimidazole dispersion into the pre-coordination complex to carry out a coordination reaction to form the shell; and drying to obtain the modified tetraazametalloporphyrin compound.

3. The reflective film according to claim 2, wherein The preparation of the modified tetraazametalloporphyrin compound includes at least one of the following features: Feature 1: The tetraazametalloporphyrin colloidal solution and the Zn in the zinc acetate 2+ The molar ratio is 1:18 to 1:22; Feature 2: The 2-methylimidazole dispersion comprises 2-methylimidazole and N,N-dimethylformamide in a mass ratio of 0.8:100 to 1.2:100; Feature 3: The volume ratio of the 2-methylimidazole dispersion to the pre-coordinated complex is 1.8:1 to 2.2:1; Feature 4: The dropping speed of the 2-methylimidazole dispersion is 0.45 L / min to 0.55 L / min; Feature 5: The dropping temperature is 20℃~30℃, and the dropping time is 6h~24h.

4. The reflective film according to claim 2, wherein The preparation of the tetraazametalloporphyrin colloidal solution comprises: dispersing the tetraazametalloporphyrin in a solvent, and performing ultrasonic treatment under ice bath conditions to form a colloid.

5. The reflective film according to claim 4, wherein The preparation of the tetraazametalloporphyrin comprises: dissolving phthalonitrile and metal chloride in a mixed solvent and refluxing under a protective atmosphere.

6. The reflective film according to claim 5, wherein The metal chloride is the chloride of the M element in the chemical formula of the tetraazametalloporphyrin; The molar ratio of the phthalonitrile to the metal chloride is 3.5:1 to 4.5:1; The mixed solvent comprises 1,8-diazabicycloundec-7-ene and 1-pentanol in a volume ratio of 1:2.5 to 1:3.5; The reflux temperature is 155°C~165°C, and the reflux time is 4h~8h.

7. A method for preparing a reflective film according to any one of claims 1 to 6, characterized in that: The following steps are involved: The coating layer is prepared on the surface of the base film.

8. The preparation method according to claim 7, characterized in that When the coating contains a modified tetraazametalloporphyrin compound, organic coating particles, an adhesive and an auxiliary agent, the preparation of the coating includes the following steps: mixing the adhesive, the organic coating particles, the auxiliary agent and a fatty acid ester solvent to obtain a first coating liquid; adding a dispersion of the modified tetraazametalloporphyrin compound to the first coating liquid, and ultrasonicating to obtain a final coating liquid; coating the final coating liquid on the surface of the base film, and thermally curing.

9. A display device, characterized in that: The display device comprises the reflective film according to any one of claims 1 to 6.

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