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WO2018127129A1 - 一种抗氧化的量子点聚合物光学膜及其制备方法和用途 - Google Patents

一种抗氧化的量子点聚合物光学膜及其制备方法和用途 Download PDF

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WO2018127129A1
WO2018127129A1 PCT/CN2018/071561 CN2018071561W WO2018127129A1 WO 2018127129 A1 WO2018127129 A1 WO 2018127129A1 CN 2018071561 W CN2018071561 W CN 2018071561W WO 2018127129 A1 WO2018127129 A1 WO 2018127129A1
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quantum dot
film
polymer
pva
quantum
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French (fr)
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肖蔓达
李沛
向振涛
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Wuhan Polyqolor Technology Ltd
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Wuhan Polyqolor Technology Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8514—Wavelength conversion means characterised by their shape, e.g. plate or foil
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8515—Wavelength conversion means not being in contact with the bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/422—Luminescent, fluorescent, phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/01—Manufacture or treatment
    • H10H20/036—Manufacture or treatment of packages
    • H10H20/0361—Manufacture or treatment of packages of wavelength conversion means

Definitions

  • the present invention relates to an oxidation-resistant photoluminescence quantum dot polymer optical film comprising a photoluminescent quantum dot nanocrystal of a core-shell structure, a polymer having low oxygen permeability, and light diffusion Agent.
  • the optical film is used in the fields of luminescence and light diffusion, such as light diffusion films, and high quality fluorescent materials for illumination and display.
  • Liquid crystal displays are widely used in personal computers, televisions, monitors, mobile phones, personal digital assistants, gaming devices, electronic reading devices, digital cameras and the like.
  • Conventional LCD devices are equipped with a backlight unit that together converts the white backlight to the desired target display color.
  • U.S. Patent No. 62,159,204 describes a one-step process for the preparation of core-shell structured photoluminescent quantum dot nanocrystals which yields large quantum dots with low cost.
  • the core-shell structured photoluminescence quantum dot nanocrystals synthesized according to this method have very strong fluorescence (quantum efficiency >70%) and are well dispersed in water due to their polyhedral shape.
  • the aqueous phase quantum dots are easily oxidized in an air environment, which reduces quantum efficiency, and generally has a stable use time of less than 6 months.
  • quantum dots synthesized in organic solvents such as TOPA/TOP and phosphorus hydride are extremely sensitive to high temperatures, intense light, oxygen, humidity, and other harmful environments.
  • US 2014/011837 on quantum dot films which discloses a quantum dot film having a three-layer composite structure comprising two barrier films on the outside to prevent moisture and oxygen from penetrating into the inner layer to destroy quantum dots.
  • the modification of the surface of the quantum dot such as plating or grafting a water-repellent oxygen barrier material such as a silica shell or an alumina shell, can make these quantum dots have water resistance.
  • CN 201480005245.1 discloses a patent for the invention of a quantum dot film encapsulated with a water-oxygen barrier film.
  • an oil-soluble quantum dot is dispersed in a system containing acrylic acid, an epoxy resin, or a photocuring agent to form an acrylic resin-based quantum dot film layer. Since the transmittance of oxygen and moisture of the acrylic resin layer is high (all are greater than 0.1 g/m 2 ⁇ day), the quantum dot film obtained by this method has unstable luminescence intensity. Therefore, the invention adopts a structure in which a two-layer water-oxygen barrier film is sandwiched with a quantum dot film to improve the luminous stability of the quantum dot film.
  • the solution for solving the stability of quantum dots of the invention has the following problems: First, the solid content of the glue must be 100%, thus limiting the range of glue selection, the optional glue is basically UV curing glue; Second, the quantum dot material It is more stable in neutral or alkaline environment, but the glue is weakly acidic, so this kind of glue is not conducive to the stability of quantum dots before curing. Third, the cost of the barrier film is very high. The cost accounts for more than half of the final product of the entire quantum dot film. Therefore, the development of inexpensive raw materials and processes to prepare quantum dot films has been a hot demand in the market.
  • the inventors have conducted extensive research and experiments and found that when a low oxygen permeability polymer is used, a quantum dot film having stable performance can be obtained without using a barrier film.
  • the present invention relates to an oxidation resistant quantum dot polymer optical film comprising: two base films, a quantum dot film sandwiched between two base films, and one or two adhesive layers, An adhesive layer is disposed between the base film and the quantum dot film, wherein the quantum dot film comprises a polymer having a low oxygen permeability, a photoluminescence quantum dot nanocrystal having a core-shell structure, and A light diffusing agent is optionally present.
  • Any polymer having low oxygen permeability can be used in the present invention, including but not limited to commercial ethylene-vinyl alcohol copolymer, polyvinyl alcohol (PVA), Resin, liquid crystal polymer, polyacrylic acid (PAA), polyvinylidene chloride, hypromellose, polyamines (such as polydiallyldimethylammonium chloride) and dicyandiamide resin, flocculant, Amphoteric polymers, polyacrylamides, polyethylene oxides, and modified derivatives of the above polymers, wherein "modification” is to further reduce the oxygen permeability of the above polymers.
  • PVA polyvinyl alcohol
  • Resin liquid crystal polymer
  • PAA polyacrylic acid
  • PAA polyvinylidene chloride
  • hypromellose polyamines (such as polydiallyldimethylammonium chloride) and dicyandiamide resin
  • flocculant such as polydiallyldimethylammonium chloride
  • the photoluminescent quantum dot nanocrystals of the core-shell structure used in the present invention include quantum dots synthesized by an aqueous phase and quantum dots synthesized by a treated oil phase.
  • the mass of the photoluminescent quantum dot nanocrystal of the core-shell structure is 0.01-10% with respect to the quantum dot film.
  • the quantum dot film has a thickness of 10 to 250 ⁇ m.
  • Light diffusing agents which can be used in the present invention include, but are not limited to, silica, titania, modified organosilicon compounds and polymer colloidal particles, preferably having a particle size of from 0.5 to 20 ⁇ m.
  • the method includes:
  • the base film in the step (5) is peeled off, and the two base films are respectively covered on the opposite faces of the peeled quantum dot film by the adhesive layer.
  • the method comprises:
  • the base film in the step (6) is peeled off, and the two base films are respectively covered on the opposite faces of the peeled quantum dot film by the adhesive layer.
  • the anti-oxidation photoluminescence polymer optical film of the invention comprises a light-diffusing agent and a core-shell structure photoluminescent quantum dot nano material, has high luminescence quantum efficiency and high optical performance, and can be applied to fluorescence and light scattering.
  • a light diffusing film for example, as a light diffusing film, a high-quality fluorescent material for illuminating and display, and a backlight module that can be stacked in a liquid crystal device
  • the invention can be applied to a liquid crystal device of a blue light source to be wider.
  • the method according to the invention has the characteristics of economy, energy saving, environmental protection, etc., and is easy to realize industrial production and mass-produce products.
  • FIG. 1(a) and 1(b) are schematic views showing the structure of a photoluminescence PVA quantum dot polymer optical film comprising a 2-layer PET base film as a support film according to the present invention, respectively.
  • Example 2 is a tensile curve showing a four-layer structure PVA quantum dot polymer optical film using a PET base film as a support film in Example 1 of the present invention.
  • Figure 3 is a graph showing the tensile curves of a single layer PVA quantum dot polymer optical film of Comparative Example 2 of the present invention.
  • the oxygen permeability data of some common polymers are listed in Table 1 below, wherein it can be seen that the oxygen permeability of polyvinyl alcohol (PVA) is relatively low, Therefore, polyvinyl alcohol is preferably used in the embodiment of the present invention.
  • PVA polyvinyl alcohol
  • a polymer having an oxygen permeability of 1.0 cc / 100 in 2 ⁇ day or less preferably a polymer having an oxygen permeability of 0.5 cc / 100 in 2 ⁇ day or less may be used.
  • Polyvinyl alcohol is an important polymer material which is obtained by alcoholysis of polyvinyl acetate. Polyvinyl alcohol molecules have a strict regular linear structure and contain a large amount of hydroxyl groups in the molecule. Therefore, polyvinyl alcohol has great hydrophilicity and is a water-soluble polymer material. Due to the presence of hydroxyl groups, polyvinyl alcohol easily forms a large number of intramolecular and intermolecular hydrogen bonds. Therefore, polyvinyl alcohol molecules have high crystallinity, chemical stability, thermal stability, light transmittance, and good gloss and high. Mechanical strength.
  • the hydroxyl group of polyvinyl alcohol determines its hydrophilic property, and in order to modify polyvinyl alcohol into a hydrophobic polymer, it is necessary to start with a hydroxyl group (-OH) after alcoholysis.
  • the chemical structure of the polyvinyl alcohol macromolecule can be changed by copolymerization modification (such as lactonization modification) and post-modification (such as acetalization reaction, esterification reaction, etc.) to obtain a hydrophobic polyvinyl alcohol polymer material. .
  • PVA has been widely used in the fields of display, food, medicine, etc.
  • PVA is used to produce polarizers for LCD devices (see US Pat. No. 8,303,867, US20020001700), which proves that it has excellent optical properties.
  • PVA films have been widely used in packaging and other industries in recent years due to their good gas barrier properties, especially for oxygen barrier properties (see US4731266).
  • Industrial methods for producing PVA films are typically cast into a film on a conveyor belt or in a flat surface. More specifically, the PVA is cast in the form of an aqueous solution onto a conveyor belt or a flat surface, and then heated and dried to form a film.
  • a photoluminescent quantum dot nanomaterial having a core-shell structure is compounded with PVA, and the prepared quantum dot composite film material has high oxygen barrier properties and optical properties.
  • PVA is present in an aqueous phase system
  • the equivalent sub-point is a quantum dot synthesized by the aqueous phase, which can obtain good dispersion in the PVA system, but for the quantum phase of the oil phase synthesis, in order to make it uniform Dispersed in the PVA system, it needs to be processed.
  • the inventors have conducted extensive research and experiments and found that the quantum dots synthesized by the oil phase are subjected to surface chemical modification. For example, when a surfactant is added, the oil phase quantum dots can be uniformly dispersed in the aqueous phase system.
  • a quantum dot synthesized from a polycarbonate having a molecular weight of 15 000 to 20 000 and an oil phase is dissolved in a dichloromethane solvent, and after mixing uniformly, the dichloromethane solvent is evaporated to obtain a solid polycarbonate.
  • a mixture of quantum dots and a ball mill pulverized to obtain a polycarbonate-coated quantum dot powder is evaporated to obtain a polycarbonate-coated quantum dot powder.
  • the quantum dot powder dispersed in the aqueous phase system prevents moisture and oxygen from penetrating into the inner layer to destroy the quantum dots.
  • an organic solvent such as DMF.
  • a quantum dot synthesized from a polycarbonate having a molecular weight of 15 000 to 20 000 and an oil phase is dissolved in a dichloromethane solvent, and uniformly mixed, and then ethyl acetate is added thereto, at this time, polycarbonate and quantum dots.
  • the mixture due to its poor solubility, quickly settles into a powdery polycarbonate-coated quantum dot solid, volatilizing the dichloromethane and ethyl acetate solvent to obtain a solid polycarbonate and quantum dot mixture powder.
  • the polymer-coated quantum dots prevent moisture and oxygen from penetrating into the inner layer to destroy the quantum dots.
  • the same purpose can be achieved by using other organic solvents having poor solubility such as DMF or ethanol.
  • the stability of the oil phase quantum dots can also be improved by adding an auxiliary agent to the quantum dots synthesized in the oil phase.
  • the auxiliary agent is a substance added to increase the oxidation resistance or stability of the quantum dots.
  • an antioxidant, an oxygen barrier material, and the like and specific examples thereof include, but are not limited to, polyethylene oxide (PEO), sodium benzoate, glutaraldehyde, and the like.
  • the method for dispersing a core-shell structured photoluminescent quantum dot nanocrystal and a light diffusing agent in an aqueous PVA solution comprises first using a light diffusing agent and a PVA aqueous solution (or a PVA dimethyl sulfoxide solution). Stirring on a high-speed disperser, and then adding the photoluminescent quantum dot nanocrystals and auxiliaries of the core-shell structure according to the formulation ratio, and dispersing on a high-speed disperser.
  • the light diffusing agent is a microsphere product developed by means of polymer polymerization technology through crosslinking, grafting functional groups, etc., and is widely used in the lighting industry, especially in the field of LED lighting. Mainly by adding inorganic or organic diffusion particles with different refractive indices in transparent plastic base materials, including inorganic particles such as SiO 2 , TiO 2 , CaCO 3 , BaSO 4 and glass beads, and polymethyl methacrylate and polyphenylene.
  • Organic polymer particles such as ethylene and silicone resin can achieve the purpose of improving the haze of the material, and convert the point and line light source into a line and a surface light source, that is, while covering the glare source, the entire resin can be made softer and more beautiful. Elegant light, opaque and comfortable.
  • Another object of the present invention to employ a light diffusing agent is to increase the path of light propagation to increase the absorption of light by quantum dots.
  • the invention relates to a method for preparing a quantum dot polymer optical film, in particular to a method for casting film comprising a quantum dot nanocrystal and a polymer having a mass percentage (nanocrystal/polymer) of 0.01-10%.
  • the solution is prepared together, then cast and dried to form a film, and the thickness of the quantum dot film after drying is between 10 and 250 ⁇ m.
  • the present inventors have confirmed that this method can produce a polymer optical film having stable optical properties and high photoluminescence quantum efficiency.
  • the film forming process according to the present invention includes a coating film and a dry film forming process.
  • the film coating method is to use a film applicator on a PET base film, the PVA quantum dot mixed solution is scraped into a uniform thickness wet film, and dried in an oven to obtain a PVA/PET double layer structure film, wherein
  • the PVA quantum dot layer has a thickness between 10 and 250 ⁇ m. Specifically, it is first dried in a forced air oven at 60-80 ° C for 3-10 min, and then dried in a vacuum drying oven at 30-50 ° C for 3-12 h to completely remove water. In the vacuum drying process, potassium hydroxide, calcium oxide or the like is used as a water absorbing agent.
  • the film forming method can prepare a quantum dot film with uniform appearance and uniform thickness, and at the same time can ensure that the quantum dots are less attenuated during the preparation process.
  • the PVA quantum dot mixed solution can be coated on the PET base film by a comma scraper, a die, a dimple, etc., and then passed through a drying unit at a temperature lower than 80 ° C, and the solvent is completely evaporated and dried.
  • the low oxygen permeability single-layer quantum dot film prepared by the method provided by the present invention has low mechanical strength due to the addition of a plasticizer auxiliary such as glycerin, phthalate or the like at a low glass transition temperature.
  • a plasticizer auxiliary such as glycerin, phthalate or the like
  • the polyvinyl alcohol single-layer quantum dot optical film which has not been modified by water resistance may be damaged by the moisture vapor erosion under high temperature and high humidity conditions.
  • the present invention improves its mechanical strength and product appearance by providing a supporting two-layer base film on the opposite side of a single-layer quantum dot film.
  • a polymer optical film having a 4-layer structure can be obtained.
  • the preparation method comprises: (1) casting a water-soluble quantum dot casting solution liquid on a surface-modified base film; 2) drying the wet film to prepare a film having a two-layer structure comprising a first base film such as PET, PMMA, PC, etc. and a PVA quantum dot optical film; (3) another surface-modified support film such as PET, PMMA, PC are coated with a glue layer; (4) The two double-layer structure films are composited to form a 4-layer composite film, as shown in Fig. 1(a). The resulting 4-layer composite film has a thickness of 50 to 350 ⁇ m.
  • the present invention confirms that this method can produce a 4-layer structure composite quantum dot polymer optical film having high photoluminescence quantum efficiency and light diffusion properties.
  • the glue for bonding the PVA quantum layer and the second base film in the method used may be a UV curing glue, a heat curing glue or the like.
  • the base film can be covered on the PVA/base film composite film, and the PVA quantum dot layer is sandwiched in the middle.
  • the UV light curing glue is squeezed in the middle with a dropper, and the glue is flattened and evenly distributed by the pressure roller.
  • the composite film prepared above is subjected to ultraviolet exposure treatment to cure the UV light curing glue to obtain a four-layer composite structure.
  • UV glue can be applied to the second base film, and then the PET/PVA quantum dot layer is bonded and UV cured to obtain a four-layer composite structure.
  • the UV light curing glue comprises a mixture of a methacrylate monomer and a photoinitiator, wherein the photoinitiator generates a radical under the excitation of ultraviolet light and induces radical polymerization of the acrylate monomer.
  • the polymer is formed and the PVA and PET are bonded together.
  • the light wave energy used in the ultraviolet exposure treatment is 8-3000 mj/cm 2 , and the exposure processing time varies depending on the exposure energy, and the range is 0.1-180 s.
  • a polymer optical film having a 5-layer structure in which a structure as shown in Fig. 1(b) is used to support a PVA film and to isolate external water vapor can be obtained.
  • the preparation method comprises: (1) casting a PVA water-soluble quantum dot casting solution liquid on an easily peelable substrate; (2) drying the wet film and peeling off the substrate to obtain a single-layer PVA quantum dot optical film; 3) Applying a layered surface of the support film such as PET, PMMA, PC to the PVA quantum dot optical film; (4) supporting the surface after another surface modification such as PET, PMMA, PC
  • the adhesive layer is coated with the other side of the composite PVA quantum dot optical film to form a composite quantum dot film having a 5-layer structure as shown in Fig. 1(b).
  • the 5-layer composite film produced has a thickness of 50-350 ⁇ m.
  • the glue used to bond the PVA quantum dot layer and the two base film in the method can be UV curing glue,
  • Example 1 Polymer optical film comprising a combination of aqueous phase synthesis quantum dots + high crystallinity PVA
  • the casting solution was deaerated in a vacuum for 12 h, then cast on a 75 ⁇ m PET base film with a surface adhesion of more than 40 dynes, and then dried in a 70 ° C blast oven for 10 min, followed by a vacuum oven at 50 ° C. Drying for 3 hours gave a dry film (PVA/PET composite structural film).
  • the obtained composite film had a full line transmittance of 85% and an initial photoluminescence quantum efficiency of 70%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, the total light transmittance was 85%, the haze was 98%, and the photoluminescence quantum efficiency was 68.5%.
  • the obtained four-layer composite film was subjected to tensile test using a universal stretching machine (Instron tester HY-30080), and the obtained tensile curve was as shown in Fig. 2, and the yield strength was 65 MPa.
  • Comparative Example 1 Polymer optical film comprising a PVA film (excluding quantum dots) compounded with a light diffusing agent
  • the obtained composite film had a light transmittance of 85%, a haze of 80%, and a photoluminescence quantum efficiency of 0%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, the total light transmittance was 85%, the haze was 80%, and the photoluminescence quantum efficiency was 0%.
  • Example 1 Compared with Comparative Example 1, the haze of the polymer optical film obtained in Example 1 was increased by 18% and the haze was 98%, indicating that almost 100% of the light transmitted from the polymer optical film was scattered, and the most The main reason is that the quantum dots absorb the light of the light source and then uniformly diverge to the surroundings, and the quantum dots act as a point source.
  • the PET base film with a surface tension of less than 25 dynes is used, and after the PVA/PET composite film is obtained, the PET base film is peeled off to obtain a quantum of only the PVA quantum dot layer. Point film.
  • the tensile test was carried out using a universal stretching machine (Instron tester HY-30080), and the obtained tensile curve is shown in Fig. 3, and the yield strength was 8 MPa.
  • the initial photoluminescence quantum efficiency of the film was 70%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, and the appearance of the sample was impaired, and the photoluminescence quantum efficiency was 60%.
  • Comparative Example 2 Compared with Comparative Example 2, the strength of the composite film of the four-layer structure of Example 1 was increased by about 7 times, and the single-layer PVA film of Comparative Example 2 was very soft, which was disadvantageous for use as an optical film in a module, but was implemented.
  • the four-layer composite structure in Example 1 can greatly increase the strength of the optical film (refer to Figs. 2 and 3) and is convenient to use.
  • Comparative Example 2 has no water-insoluble PET base film protection on both sides of the PVA film, so the water vapor is eroded at 85% relative humidity. The appearance of the film was impaired, but the composite film of the four-layer structure was not damaged in appearance under the conditions.
  • the quantum dot film of Comparative Example 2 was attenuated by 8.5 percentage points after 100 h at 85% RH.
  • Example 2 Polymer optical film comprising a combination of aqueous phase synthesis quantum dots + low crystallinity PVA
  • the obtained composite film had a light transmittance of 85%, a haze of 98%, and an initial photoluminescence quantum efficiency of 70%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, the total light transmittance was 85%, the haze was 98%, and the photoluminescence quantum efficiency was 58%.
  • Example 3 Polymer optical film comprising an oil phase synthetic quantum dot powder + PVA combination
  • a powder of an oil phase synthetic quantum dot is prepared, and 10 parts by mass of a polycarbonate material having an molecular weight of 15000 to 20,000 and an oil phase synthesized with a quantum dot material (1.0 parts by mass of a green quantum dot, a peak position of 520 nm, and 0.25 parts by mass of a red quantum dot) , peak position 625nm, provided by Tianjin Nanocomy) dissolved in methylene chloride solvent, mixed uniformly and then volatilized solvent to obtain a solid polycarbonate and quantum dot mixture, after ball milling and pulverization to obtain polymer coated oil phase synthesis Quantum dot powder.
  • a quantum dot material 1.0 parts by mass of a green quantum dot, a peak position of 520 nm, and 0.25 parts by mass of a red quantum dot
  • peak position 625nm provided by Tianjin Nanocomy
  • a PVA polymer PVA having a degree of alcoholysis of 98.0 mol% and a degree of polymerization of 2,700
  • 10 parts by mass of glycerin were dissolved in water, and it took 2 hours to dissolve at a temperature of 90 °C.
  • 7.5 parts by mass of silicone particles having a particle diameter of 10 ⁇ m were dispersed in a PVA solution by a disperser at a dispersion speed of 1200 rpm.
  • the oil phase quantum dot powder prepared above was dispersed in a PVA solution to form a casting solution at a dispersion speed of 1200 rpm.
  • the casting solution contains 75% by mass of volatile water.
  • the casting solution was degassed in a vacuum for 12 h, then cast on a surface-modified PET base film having a thickness of 75 ⁇ m, dried in a 70 ° C blast oven for 10 min, and dried in a vacuum oven at 50 ° C for 3 h. Dry film. Then, another PET base film having a thickness of 75 ⁇ m which was not easily peeled off after surface modification was overlaid on the PVA/PET film to sandwich the PVA quantum dot layer. Then, the UV light curing glue is squeezed in the middle with a dropper, the glue is flattened by a pressure roller and evenly distributed between the PVA and the PET base film, and the composite film prepared above is subjected to ultraviolet exposure treatment. The gel was cured by exposure to UV light having an energy of 8 W/cm 2 for 180 s to obtain a polymer optical film of a four-layer composite structure in which the thickness of the quantum dot layer was 40 ⁇ m.
  • the initial photoluminescence quantum efficiency of the obtained polymer optical film was 72%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, and the photoluminescence quantum efficiency was reduced to 65%.
  • Example 4 Polymer optical film comprising an oil phase synthetic quantum dot powder + PVA combination
  • the initial photoluminescence quantum efficiency of the obtained polymer optical film was 72%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, and the photoluminescence quantum efficiency was reduced to 65%.
  • Example 4 The photoluminescence quantum efficiency of the polymer optical film obtained in Example 4 and Example 3 was the same, indicating that the above two methods for treating quantum dots synthesized by the oil phase did not have much influence on the performance of the quantum dots.
  • a UV glue quantum dot film with a quantum dot layer thickness of 40 ⁇ m was prepared.
  • This method uses quantum dot nanocrystals synthesized by an oil phase, and the acrylic resin used is an amorphous polymer material.
  • the dispersion machine (Dragon Lab OS20-S) rotates at 1800 rpm, the turntable diameter is 30 mm, and the dispersion time is 10 min.
  • the photoluminescence quantum efficiency of the obtained polymer optical film was 68%.
  • the polymer optical film was allowed to stand at a temperature of 85 ° C and 85% RH for 100 h, and the photoluminescence quantum efficiency was 50%.
  • the quantum luminescence efficiency of the polymer optical film is higher than that of Comparative Example 3.
  • the main reason is that the quantum luminescence efficiency of quantum dots is proportional to the refractive index of the dispersion medium.
  • the refractive index of PVA is higher than that of acrylic resin, resulting in higher luminous efficiency of quantum dots finally dispersed in the PVA film.
  • the quantum dot luminescence efficiency of the quantum dot film of Example 1 was only attenuated by 1.5% over 100 h, Example 2 was attenuated by 12%, and Comparative Example 3 quantum dot film The quantum dot luminescence efficiency is attenuated by 18%. It shows that PVA polymer material with high crystallinity has very good oxygen barrier property; and PVA with low crystallinity also has certain oxygen barrier property, which leads to delay of quantum dot luminous efficiency decay.
  • the initial photoluminescence quantum efficiency of the polymer optical film of Example 3 is 4 percentage points higher, which is mainly because the quantum luminous efficiency of the quantum dot is proportional to the refractive index of the dispersion medium, and the refractive index of the PVA The rate is higher than that of the acrylic resin, resulting in a higher luminous efficiency of the quantum dots finally dispersed in the PVA film.
  • the quantum luminescence efficiency of Example 3 is more stable, and the sample is only attenuated by 7 percentage points at 85 ° C and 85% RH for 100 h, while the quantum luminescence efficiency of Comparative Example 3 is attenuated by 18 percentage points, further demonstrating that the crystalline polymer can Improve the stability of quantum dots.
  • Example 5 Polymer optical film comprising oil phase synthesis quantum dot + polyoxyethylene (PEO) auxiliary + PVA
  • PVA polymer Extrapolymer-based polymer (Mowiol 24-88 alcoholysis degree 88.0 mol%, polymerization degree 3200, supplied by Sigma-Aldrich), 20 parts by mass of PEO (1,000,000 molecular weight, supplied by BASF) were dissolved in water at a temperature of 90 ° C. It takes 2.5 hours to dissolve. Then, 7.50 parts by mass of silicone particles having a particle diameter of 10 ⁇ m (elected by EL202A, supplied by a singular material) were dispersed in the above PVA solution by a disperser at a dispersion speed of 1200 rpm.
  • PVA polymer Extrapolysis degree 88.0 mol%, polymerization degree 3200, supplied by Sigma-Aldrich
  • PEO 1,000,000 molecular weight
  • the obtained polymer optical film had a full line transmittance of 88%, a haze of 98%, and an initial photoluminescence quantum efficiency of 77%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, and the photoluminescence quantum efficiency was 72.6%.
  • the initial quantum dot efficiency of the polymer optical film of Example 5 is 9 percentage points higher, which is mainly because the quantum luminous efficiency of the quantum dot is proportional to the refractive index of the dispersion medium, and the refractive index of the PVA is higher.
  • the high acrylic resin leads to higher luminous efficiency of quantum dots finally dispersed in the PVA film.
  • PEO can be bonded to PVA through hydrogen bonding and embedded in the amorphous segment of PVA to form a denser structure. Increased barrier properties.
  • the quantum dot luminous efficiency of the polymer optical film of Example 5 was attenuated by 4.4%, while the quantum dot luminous efficiency of the polymeric optical film of Comparative Example 3 was attenuated by 18%. It proves that PVA polymer material blended with PEO solution has better anti-attenuation performance.
  • Example 6 Polymer optical film comprising oil phase synthesis quantum dot + glutaraldehyde adjuvant + PVA
  • red core-shell structured photoluminescent quantum dot nanocrystals and 1.0 part by mass of green core-shell structured photoluminescent quantum dot nanocrystals are dispersed into the above PVA solution to form a casting solution.
  • the stirring speed was 800 rpm.
  • a glutaraldehyde hydrochloride mixed solution (containing 5 parts by mass of a 10% aqueous solution of glutaraldehyde and 0.5 part by mass of a 1.0 mol/L aqueous hydrochloric acid solution) was dispersed in a casting solution at a stirring speed of 500 rpm.
  • the casting solution contains 75% by mass of volatile water.
  • the casting solution was degassed in a vacuum for 12 h, then cast on a surface-modified 75 ⁇ m thick PET base film, dried in a 70 ° C blast oven for 10 min, and then dried in a vacuum oven at 50 ° C for 3 h.
  • a dry film (PVA/PET composite structural film) was obtained.
  • the obtained composite film had a light transmittance of 88%, a haze of 98%, and an initial photoluminescence quantum efficiency of 75%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, and the photoluminescence quantum efficiency was 69%.
  • the initial quantum dot efficiency of the polymer optical film of Example 6 is 7 percentage points higher, which is mainly because the quantum luminous efficiency of the quantum dot is proportional to the refractive index of the dispersion medium, and the refractive index of the PVA is higher.
  • the high acrylic resin leads to higher luminous efficiency of the quantum dots finally dispersed in the PVA film.
  • glutaraldehyde reacts with PVA under the catalysis of hydrochloric acid to form a moderate cross-linking structure, making the PVA water resistant. Sexuality has been improved, and it is difficult for water vapor to penetrate into the interior of PVA to affect quantum dots.
  • Example 7 Polymer optical film comprising an oil phase synthetic quantum dot + high crystallinity PVA combination
  • the casting solution was deaerated in a vacuum for 12 h, then cast on a PET base film having a surface adhesion of more than 40 dynes having a thickness of 75 ⁇ m, dried in a 70 ° C blast oven for 10 min, and then vacuum dried at 50 ° C. Drying in a box for 3 hours gave a dry film (PVA/PET composite structural film).
  • the obtained composite film had a full line transmittance of 85% and an initial photoluminescence quantum efficiency of 70%.
  • the sample was placed at 85 ° C, 85% RH for 100 h, the total light transmittance was 85%, the haze was 98%, and the photoluminescence quantum efficiency was 68.5%.

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Abstract

一种抗氧化的量子点聚合物光学膜、其制备方法及其在发光、光扩散方面的应用，例如用作光扩散膜，以及照明和显示用的高质量荧光材料等。该聚合物光学膜包含核壳结构的光致发光量子点纳米晶体和具有低氧气渗透率的聚合物，同时也可通过添加光扩散剂达到更好的显示效果。

Description

一种抗氧化的量子点聚合物光学膜及其制备方法和用途 技术领域
本发明涉及一种抗氧化的光致发荧光量子点聚合物光学膜，所述聚合物光学膜包含核壳结构的光致发光的量子点纳米晶体、具有低氧气渗透率的聚合物以及光扩散剂。该光学薄膜应用于发光和光扩散领域，比如用作光扩散膜，以及照明和显示用的高质量荧光材料。
背景技术
液晶显示器被广泛应用在个人电脑、电视、监视器、移动电话、个人数码助手、游戏设备、电子阅读设备、数码相机等类似领域。传统的LCD设备均配备一个背光单元，它们一起将白色的背光转换成所需要的目标显示颜色。
美国专利62159204描述了制备核壳结构光致发光量子点纳米晶体的一步法，该方法所得到的量子点产量大、成本低。按此法合成的核壳结构光致发光量子点纳米晶体具有非常强的荧光(量子效率>70％)，同时由于其多面体形状使之能在水中分散很好。但是，该水相量子点在空气环境中易被氧化，使量子效率降低，一般其稳定使用时间在6个月以下。
US2012/0113672、US2014/011837以及许多其他研究表明，在TOPA/TOP和三氢化磷等有机溶剂中合成的量子点对高温、强光、氧气、湿度及其它有害环境极为敏感。关于量子点膜的US 2014/011837，声明了一种具有3层复合结构的量子点薄膜，它包含了在外侧的两张阻隔膜，以阻止湿气和氧气渗透到内层破坏量子点。此外，对量子点表面进行修饰如镀上或嫁接二氧化硅壳、氧化铝壳等隔水隔氧材料，可以让这些量子点具有耐水性能。
CN 201480005245.1公布了一项采用水氧阻隔膜进行封装的量子点膜的发明专利。该发明将油溶性的量子点分散在含丙烯酸、环氧树脂、光固化剂的体系中制成丙烯酸树脂类量子点膜层。由于丙烯酸树脂层的氧气、水气的透过率较高(均大于0.1g/m 2·day)，此法得到的量子点膜层发光强度不稳定。因此，该发明采用了两层水氧阻隔膜夹一层量子点膜的结构，来提高量子点膜发光稳定性。但该发明所述解决量子点稳定性的方案存在如下问题：一，要求胶水固含量必须是100％，因此限定了胶水选择的范围，可选的胶水基本为UV固化胶水；二，量子点材料在中性或碱性环境更加稳定，但该类胶水是弱酸性的，因此该类胶水在固化前本质上是不利于量子点稳定性的；三，所采用阻隔膜的成本很高，该原材料成本占了整个量子点膜最终产品的一半以上。因此，开发廉价的原材料以及工艺方法来制备量子点膜一直是市场的热门需求。
发明内容
针对现有技术中的上述缺陷，本发明人经过大量的研究和实验，发现当采用低透氧性的聚合物时，不需要采用阻隔膜就能得到性能稳定的量子点薄膜。
本发明涉及一种抗氧化的量子点聚合物光学膜，所述光学膜包含：两层基膜，夹在两层基膜中间的量子点膜，和一个或两个粘合剂层，所述粘合剂层位于所述基膜和所述量子点膜之间，其特征在于：所述量子点膜包含具有低氧气渗透率的聚合物、核壳结构的光致发光的量子点纳米晶体和任选存在的光扩散剂。
在本发明中可以使用任何具有低氧气渗透性的聚合物，包括但不限于商业化的乙烯-乙烯醇共聚物、聚乙烯醇(PVA)、
Figure PCTCN2018071561-appb-000001
树脂、液晶聚合物、聚丙烯酸(PAA)、聚偏二氯乙烯、羟丙甲纤维素、聚胺类(如聚二烯丙基二甲基氯化铵)和双氰胺树脂、絮凝剂、两性高分子、聚丙烯酰胺、聚氧化乙烯以及上述聚合物的改性衍生物，其中的“改性”是为了使上述聚合物的氧气渗透率进一步降低。
在本发明中所使用的核壳结构的光致发光的量子点纳米晶体包括水相合成的量子点和经处理的油相合成的量子点。优选地，相对于所述量子点膜，所述核壳结构的光致发光的量子点纳米晶体的质量为0.01-10％。优选的，所述量子点膜的厚度为10-250μm。
在本发明中可以使用的光扩散剂包括但不限于二氧化硅、二氧化钛、改性有机硅化合物和聚合物胶体粒子，优选的，粒径为0.5-20μm。
关于本发明的聚合物光学膜的制备方法，在使用水相合成的核壳结构的光致发光的量子点纳米晶体的情况下，所述方法包括：
(1)用水或二甲基亚砜作为溶剂溶解具有低氧气渗透率的聚合物；
(2)任选地，将光扩散剂分散入具有低氧气渗透率的聚合物溶液中；
(3)将水相合成的核壳结构的光致发光的量子点纳米晶体分散到所溶聚合物中；
(4)上述混合物经过脱泡工艺，形成铸膜液；
(5)在基膜上流延，干燥成膜；
(6)将另一基膜通过粘合剂层覆盖在上述形成的量子点膜上。
或者，在步骤(6)中，剥离掉步骤(5)中的基膜，通过粘合剂层分别将两层基膜覆盖在剥离后的量子点膜的相对面上。
而在使用油相合成的核壳结构的光致发光的量子点纳米晶体和低氧气渗透率的聚合物的情况下，所述方法包括：
(1)将油相合成的核壳结构的光致发光的量子点纳米晶体进行预处理，所述预处理包括将量子点纳米晶体混合入疏水的聚合物中，制成量子点粉末，或者在量子点纳米晶体中加入选自抗氧化剂和阻氧材料中的一种或多种以进一步提高油相量子点稳定性；
(2)用水或二甲基亚砜作为溶剂溶解具有低氧气渗透率的聚合物；
(3)任选地，将光扩散剂分散入具有低氧气渗透率的聚合物溶液中；
(4)将上述经预处理的油相合成的核壳结构的光致发光的量子点纳米晶体分散到所溶聚合物中；
(5)上述混合物经过脱泡工艺，形成铸膜液；
(6)在基膜上流延，干燥成膜；
(7)将另一基膜通过粘合剂层覆盖在上述形成的量子点膜上。
或者，在步骤(7)中，剥离掉步骤(6)中的基膜，通过粘合剂层分别将两层基膜覆盖在剥离后的量子点膜的相对面上。
本发明所涉及的抗氧化的光致发荧光的聚合物光学膜包含了光扩散剂和核壳结构的光致发光量子点纳米材料，具有高发光量子效率和高光学性能，可应用在荧光和光散射等领域，例如用作光扩散膜、用于发光和显示方面的高质量荧光材料、以及可叠入液晶设备的背光模组中，将本发明应用到蓝色光源的液晶设备中可以得到更广的色域范围。本发明所涉及到的方法，具有经济、节能、环保等特点，并且容易实现工业化生产，批量制备产品。
附图说明
通过阅读以下发明详述并结合附图，本领域技术人员很容易理解本发明的上述目的和优点。
图1(a)和(b)是分别显示本发明所涉及的包含2层PET基膜作为支撑膜的光致发光PVA量子点聚合物光学膜的结构示意图。
图2是显示本发明实施例1中的采用PET基膜作为支撑膜的四层结构PVA量子点聚合物光学膜的拉伸曲线。
图3是显示本发明对比例2的单层PVA量子点聚合物光学膜的拉伸曲线。
具体实施方式
关于本发明中所使用的低氧气渗透率的聚合物，如下表1列出了一些常见聚合物的氧气渗透性数据，其中，可以看出聚乙烯醇(PVA)的氧气渗透性相对较低，因此，聚乙烯醇在本发明的实施方式中被优选使用。
表1：厚度为25μm的结晶聚合物薄膜的氧气渗透性
材料 O 2TR(cc/100in 2·day) 备注
聚丙烯腈 0.7 单层膜
聚乙烯乙烯醇 <0.12 单层膜
聚乙烯醇 0.02-0.2 在PET上涂聚乙烯醇
PET 4.5 单层膜
定向尼龙 3 单层膜
液晶聚合物 0.04 单层膜
聚二氯乙烯 0.5-1.3 在基膜上涂聚二氯乙烯
对于在本发明中的应用，可以使用氧气渗透性为1.0cc/100in 2·day或以下的聚合物，优选氧气渗透性为0.5cc/100in 2·day或以下的聚合物。
聚乙烯醇是一种重要的高分子材料，它是由聚醋酸乙烯酯醇解得到的。聚乙烯醇分子 具有严格的规整线性结构，分子内含有大量的羟基，因此聚乙烯醇具有极大的亲水性，是一种水溶性高分子材料。由于羟基的存在，聚乙烯醇易形成大量的分子内和分子间氢键，因此，聚乙烯醇分子具有高度的结晶性、化学稳定性、热稳定性、透光性以及良好的光泽和高的机械强度。聚乙烯醇的羟基决定了其亲水性能，为了将聚乙烯醇改性为疏水聚合物，需要从醇解后的羟基(-OH)入手。可以通过共聚改性(如内酯化改性)和后期改性(如缩醛化反应、酯化反应等)来改变聚乙烯醇大分子的化学结构，获得疏水性的聚乙烯醇聚合物材料。
PVA已被广泛应用在显示、食品、医药等领域，例如，PVA被用来生产LCD设备的偏光片(参见US8303867，US20020001700)，证明其具有很好的光学性能。此外，由于PVA膜具有良好的气体阻隔性，尤其是对氧气的阻隔性优异等特点，近些年PVA膜被广泛应用于包装等行业(参见US4731266)。工业上生产PVA膜的方法通常是在传送带或平面上流延成膜。更具体的，PVA是以水溶液形式被流延到传送带或平面上，之后加热烘干成膜。
本发明人进一步出人意料地发现，将具有核壳结构的光致发光量子点纳米材料与PVA复合，制备出的量子点复合膜材料具有较高的阻氧性能和光学性能。考虑到PVA是以水相体系存在，当量子点是水相合成的量子点时，其能够在PVA体系中获得良好的分散，但是对于油相合成的量子点而言，为了使其能够均匀地分散于PVA体系中，需要对其进行处理。
本发明人经过大量研究和实验，发现对油相合成的量子点进行表面化学方法修饰，如加入表面活性剂时，可以将油相量子点均匀地分散在水相体系中。
除了表面化学方法修饰之外，为了使油相合成的量子点能够均匀地分散于PVA体系中，本发明人还研究得到了另一种增强油相量子点的耐水性且在水相体系均匀分散的方法。在一种实施方式中，将分子量为15 000-20 000的聚碳酸酯和油相合成的量子点溶解在二氯甲烷溶剂中，混合均匀后挥发掉二氯甲烷溶剂，获得固体的聚碳酸酯和量子点混合物，经过球磨粉碎后获得聚碳酸酯包覆的量子点粉末。采用这种包覆技术后，分散在水相体系的量子点粉末可以阻止水汽和氧气渗透到内层破坏量子点。用DMF等有机溶剂也可以达到相同的目的。
与上述方法类似，为了使油相合成的量子点能够均匀地分散于PVA水相体系中，本发明人还研究得到了另一种增强油相量子点耐水性且在水相体系均匀分散的方法。在一种实施方式中，将分子量为15 000-20 000的聚碳酸酯和油相合成的量子点溶解在二氯甲烷溶剂中，混合均匀后加入乙酸乙酯，此时聚碳酸酯和量子点混合物由于其溶解度差，会迅速沉降成粉末状的聚碳酸酯包覆的量子点固体，挥发掉二氯甲烷和乙酸乙酯溶剂后获得固体的聚碳酸酯和量子点混合物粉末。此聚合物包覆的量子点可阻止水汽和氧气渗透到内层破坏量子点。用DMF、乙醇等其它溶解度差的有机溶剂也可以达到相同的目的。
另外，通过在油相合成的量子点中加入助剂也可以提高油相量子点的稳定性，在本发明的上下文中，助剂是为了增加量子点的抗氧化性或稳定性而添加的物质，例如抗氧化剂、阻氧材料等，其具体例子包括但不限于：聚氧化乙烯(PEO)、苯甲酸钠、戊二醛等。具 体的说，本发明所涉及的将核壳结构的光致发光量子点纳米晶体和光扩散剂分散在PVA水溶液中的方法包括，先将光扩散剂与PVA水溶液(或PVA二甲基亚砜溶液)在高速分散机上搅拌，之后按配方比例加入核壳结构的光致发光量子点纳米晶体及助剂，在高速分散机上分散。
光扩散剂是利用高分子聚合技术，通过交联、接枝官能团等手段开发的微球类产品，其在照明行业尤其是LED照明领域得到广泛应用。主要通过在透明塑料基料中加入具有不同折射率的无机或有机扩散粒子，包括SiO 2、TiO 2、CaCO 3、BaSO 4和玻璃微珠等无机微粒，以及聚甲基丙烯酸甲酯、聚苯乙烯、硅树脂等有机聚合物微粒，达到提高材料雾度的目的，将点、线光源转换成线、面光源，即在遮住刺眼光源的同时，又能使整个树脂发出更加柔和、美观、高雅的光，达到透光不透明的舒适效果。本发明采用光扩散剂的另一个目的是为了改变光传播的路径来增加量子点对光的吸收。
本发明涉及的量子点聚合物光学膜的制备方法，具体涉及一种流延制膜的方法，其包括将质量百分比(纳米晶体/聚合物)为0.01-10％的量子点纳米晶体与聚合物一起制成溶液，然后流延、烘干成膜，干燥后量子点膜的厚度在10-250μm之间。同时，本发明确认此法可制备得到光学性能稳定且光致发光量子效率高的聚合物光学膜。
本发明所涉及的制膜工艺包括涂膜和干燥成膜过程。
在实验室，涂膜方法为使用涂膜器在PET基膜上，将PVA量子点混合溶液刮涂成厚度均一的湿膜，并在烘箱中干燥成型，得到PVA/PET双层结构薄膜，其中PVA量子点层厚度在10-250μm之间。具体的，先在鼓风烘箱中以60-80℃干燥3-10min，之后于真空干燥箱中以30-50℃干燥3-12h以彻底除水。真空干燥过程中，用氢氧化钾、氧化钙等作为吸水剂。此制膜方法可以制备外观平整，厚度均一的量子点膜，同时可以保证量子点在制备过程中衰减程度较小。
在生产线上，可以采用逗号刮刀、模头、微凹等涂布方式将PVA量子点混合溶液涂在PET基膜上，然后经过烘干单元，温度低于80℃，待溶剂挥发完全，干燥得到PVA/PET双层结构薄膜，其中PVA量子点层厚度在10-250μm之间。
由本发明提供的方法制备得到的低氧气渗透率的单层量子点膜，由于加入了塑化剂助剂例如甘油、酞酸酯等低玻璃化温度的有机物质，其机械强度较低。此外，未经耐水改性的聚乙烯醇单层量子点光学膜在高温高湿条件下由于水汽的侵蚀，会使产品外观受损。为此，本发明通过在单层量子点膜的相对面上设置起支撑作用的两层基膜来改善其机械强度和产品外观。
根据本发明提供的制备方法，可以得到具有4层结构的聚合物光学膜，具体的，所述制备方法包括：(1)在经过表面修饰的基膜上流延水溶性量子点铸膜液；(2)干燥湿膜来制备具有双层结构的薄膜，该膜包含第一基膜如PET、PMMA、PC等和PVA量子点光学膜；(3)在另一张经表面修饰后的支撑膜如PET、PMMA、PC上涂上胶层；(4)复合这两种双层结构膜，形成4层结构的复合薄膜，见图1(a)。所得4层结构复合膜厚度为50-350μm。本发明确认此法可制备得到具有高光致发光量子效率和光扩散性能的4层结构复合量子点 聚合物光学膜。所采用的方法中粘结PVA量子层与第二层基膜的胶水可为UV固化胶水、热固化胶水等。实验室制作时，可将基膜覆盖在PVA/基膜组合膜上，PVA量子点层夹在中间，之后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA量子点层与基膜之间，将上述制备的复合膜进行紫外曝光处理，使UV光固化胶水固化，得到四层复合结构。生产线上，可将UV胶水涂在第二基膜上，然后贴合PET/PVA量子点层，同时UV固化，得到四层复合结构。所述的UV光固化胶水包括甲基丙烯酸酯类单体及光引发剂组成的混合物，其中光引发剂可在紫外光的激发下产生自由基，并诱导丙烯酸酯类单体进行自由基聚合，形成聚合物，将PVA和PET粘在一起。所述紫外曝光处理所采用的光波能量为8-3000mj/cm 2，曝光处理时间根据曝光能量大小而不同，范围为0.1-180s。
根据本发明提供的制备方法，可以得到具有5层结构的聚合物光学膜，其中采用如图1(b)所示的结构来支撑PVA薄膜和隔离外界水汽。具体的，所述制备方法包括：(1)在经过易剥离的基板上流延PVA水溶性量子点铸膜液；(2)干燥湿膜后从基板上剥离得到单层PVA量子点光学膜；(3)在一张经表面修饰后的支撑膜如PET、PMMA、PC上涂上胶层复合PVA量子点光学膜；(4)在另一张经表面修饰后的支撑膜如PET、PMMA、PC上涂上胶层，复合PVA量子点光学膜的另一面，形成如图1(b)所示的5层结构的复合量子点薄膜。所制5层结构复合膜厚度为50-350μm。同理，所采用的方法中粘结PVA量子点层与两层基膜的胶水可为UV固化胶水、热固化胶水等。
实施例
实施例1：包含水相合成量子点+高结晶度PVA组合的聚合物光学膜
首先，将100质量份PVA聚合物(Mowiol 18-98，高结晶度，醇解度98.0mol％，聚合度2700，Sigma-Aldrich提供)和10质量份甘油溶解在水中，温度90℃时溶解需要2h。然后用分散机将7.5质量份粒径为10μm的有机硅粒子(EL202A，涌奇材料提供)分散到PVA溶液中，分散速度1200rpm。最后，将1.0质量份绿色核壳结构光致发光量子点纳米晶体和0.25质量份红色核壳结构光致发光量子点纳米晶体(水相量子点，南京大学邓正涛教授研发组提供，初始量子点发光效率70％)分散到PVA溶液中形成铸膜液，搅拌速度200rpm，该铸膜液含有75％质量份的挥发水份。再将铸膜液在真空中脱气泡12h，随后在75μm的表面附着力大于40达因的PET基膜上流延成型，再在70℃鼓风烘箱中干燥10min，随后在50℃真空干燥箱中干燥3h得到干膜(PVA/PET复合结构薄膜)。
然后，将另一张经过表面修饰后不易剥离的厚度同为75μm的PET基膜覆盖在PVA/PET膜上，使PVA量子点层夹在中间。然后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA与PET基膜之间，将上述制备的复合膜进行紫外曝光处理。使用能量为8W/cm 2的UV光曝光180s，使胶水固化，得到四层复合结构，该结构如图1(a)所示。
所得复合膜全线透光率为85％，初始光致发光量子效率为70％。样品在85℃温度、85％RH条件下放置100h，全光线透光率为85％，雾度98％，光致发光量子效率为68.5％。
所得四层结构复合膜用万用拉伸机(英斯特朗试验机HY-30080)进行拉伸测试，所 得拉伸曲线如图2所示，屈服强度为65MPa。
对比例1：包含复合了光扩散剂的PVA膜(不包含量子点)的聚合物光学膜
与实施例1的方法基本完全一致，不同点为在PVA/PET复合结构薄膜的制备过程中，不加入任何量子点，以及PVA光扩散膜的混合液具有65％质量份数的挥发水份。
所得复合膜全线透光率为85％，雾度80％，光致发光量子效率为0％。样品在85℃温度、85％RH条件下放置100h，全光线透光率为85％，雾度80％，光致发光量子效率为0％。
与对比例1相比，实施例1所得聚合物光学膜的雾度增加了18％，雾度达到98％，说明从聚合物光学膜透过来的光，几乎100％都发生了散射，其最主要的原因是量子点吸收了光源的光，然后向周围均匀发散，量子点此时起到了点光源的作用。
对比例2：只有PVA层的聚合物光学膜
与实施例1的方法基本完全一致，不同点为采用表面张力小于25达因的PET基膜，并在制得PVA/PET复合膜后，将PET基膜剥离，得到只有PVA量子点层的量子点膜。用万用拉伸机(英斯特朗试验机HY-30080)进行拉伸测试，所得拉伸曲线如图3所示，屈服强度为8MPa。
该膜初始光致发光量子效率为70％。样品在85℃温度、85％RH条件下放置100h，样品外观受损，光致发光量子效率为60％。
与对比例2相比，实施例1的四层结构的复合膜的强度上升了7倍左右，对比例2的单层PVA膜非常柔软，作为光学膜不利于在模组中使用，但是采用实施例1中的四层复合结构，可以极大提高光学膜的强度(参考图2与图3)，便于使用。此外，由于所使用的醇解度98％的PVA具有一定的水溶性，对比例2由于PVA膜两面没有非水溶性的PET基膜保护，所以在85％相对湿度条件下由于水汽的侵蚀，量子点膜外观受损，但四层结构的复合膜在该条件下外观就没有受损。此外，由于水汽直接侵蚀，对比例2的量子点膜在85％RH条件下100h后发光效率多衰减了8.5个百分点。
实施例2：包含水相合成量子点+低结晶度PVA组合的聚合物光学膜
首先，将100质量份PVA聚合物(Mowiol 4-88，低结晶度，醇解度88.0mol％，聚合度630，Sigma-Aldrich提供)和10质量份甘油溶解在水中，温度90℃时溶解需要0.5h。然后用分散机将7.5质量份粒径为10μm的有机硅粒子(EL202A，涌奇材料提供)分散到PVA溶液中，分散速度1600rpm。最后，将1.0质量份绿色核壳结构光致发光量子点纳米晶体和0.25质量份红色核壳结构光致发光量子点纳米晶体(水相量子点，南京大学邓正涛教授研发组提供，初始量子点发光效率70％)分散到PVA溶液中形成铸膜液，搅拌速度200rpm，该铸膜液含有75％质量份数的挥发水份。再将铸膜液在真空中脱气泡12h， 随后在75μm的表面张力大于40达因的PET基膜上流延成型，再在70℃鼓风烘箱中干燥10min，然后在50℃真空干燥箱中干燥3h得到干膜(PVA/PET复合结构薄膜)。
然后，将另一张经过表面修饰后不易剥离的厚度同为75μm的PET基膜覆盖在PVA/PET膜上，使PVA量子点层夹在中间。然后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA与PET基膜之间，将上述制备的复合膜进行紫外曝光处理。使用能量为8W/cm 2的UV光曝光180s，使胶水固化，得到四层复合结构。
所得复合膜全线透光率为85％，雾度98％，初始光致发光量子效率为70％。样品在85℃温度、85％RH条件下放置100h，全光线透光率为85％，雾度98％，光致发光量子效率为58％。
实施例3：包含油相合成量子点粉末+PVA组合的聚合物光学膜
首先，制备油相合成量子点的粉末，将10质量份分子量为15000-20000的聚碳酸酯和油相合成的量子点材料(1.0质量份绿色量子点，峰位520nm和0.25质量份红色量子点，峰位625nm，均由天津Nanocomy提供)溶解在二氯甲烷溶剂中，混合均匀后挥发掉溶剂，获得固体的聚碳酸酯和量子点混合物，经过球磨粉碎后获得聚合物包覆的油相合成的量子点粉末。
接下来，生产制备复合了上述量子点粉末及光扩散剂的PVA光学膜。
首先，将80质量份的PVA聚合物(醇解度98.0mol％、聚合度2700的PVA)和10质量份数甘油溶解在水中，温度90℃时溶解需要2h。然后用分散机将7.5质量份的粒径为10μm的有机硅粒子分散到PVA溶液中，分散速度1200rpm。最后，将上述制备的油相量子点粉末分散到PVA溶液中形成铸膜液，分散速度1200rpm。该铸膜液含有75％质量份数的挥发水份。再将铸膜液在真空中脱气泡12h，随后在经表面修饰的厚度为75μm的PET基膜上流延成型，再在70℃鼓风烘箱中干燥10min，在50℃真空干燥箱中干燥3h得到干膜。然后，将另一张经过表面修饰后不易剥离的厚度同为75μm的PET基膜覆盖在PVA/PET膜上，使PVA量子点层夹在中间。然后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA与PET基膜之间，将上述制备的复合膜进行紫外曝光处理。使用能量为8W/cm 2的UV光曝光180s，使胶水固化，得到四层复合结构的聚合物光学膜，其中，量子点层的厚度为40μm。
所得聚合物光学膜的初始光致发光量子效率为72％。样品在85℃温度、85％RH条件下放置100h，光致发光量子效率降为65％。
实施例4：包含油相合成量子点粉末+PVA组合的聚合物光学膜
与实施例3的方法基本完全一致，不同点为选用如下的油相合成的量子点的处理方法：将10质量份分子量为15000-20000的聚碳酸酯和油相合成的量子点材料(1.0质量份绿色量子点，峰位520nm和0.25质量份红色量子点，峰位625nm，均由天津Nanocomy提供)溶解在二氯甲烷溶剂中，混合均匀后加入乙酸乙酯，此时聚碳酸酯和量子点的混合物由于溶解度差，会迅速沉降，分离干燥后获得固体的聚碳酸酯和量子点混合物粉末，此即油相合成的量子点粉末。
所得聚合物光学膜的初始光致发光量子效率为72％。样品在85℃温度、85％RH条件 下放置100h，光致发光量子效率降为65％。
实施例4与实施例3获得的聚合物光学膜的光致发光量子效率相同，说明了上述两种对于油相合成的量子点的处理方法未对量子点的性能带来太大影响。
对比例3：包含油相合成的量子点材料+丙烯酸树脂类UV胶水的聚合物光学膜
本着对比和研究的目的，制备了量子点层厚度为40μm的UV胶水量子点膜。该方法使用油相合成的量子点纳米晶体，所采用丙烯酸树脂属于非结晶高分子材料。将7.5质量份(与所有实施例保持相同的总质量含量)的光扩散粒子分散到100质量份含有丙烯酸树脂、环氧树脂和光引发剂的聚合物材料(BTW-504-33，东莞贝特利新材料有限公司提供)中，分散机(Dragon Lab OS20-S)转速1800rpm，转盘直径30mm，分散时间10min。然后，加入1.0质量份绿色量子点(由天津Nanocomy提供，峰位520nm，初始量子点发光效率80％)和0.25质量份红色量子点(由天津Nanocomy提供，峰位625nm，初始量子点发光效率85％)，混合形成含有绿色和红色量子点的UV固化胶水。将此量子点胶水涂在厚度为75μm的PET基膜上，贴合另一层厚度为75μm的PET基膜后，在385nm的UV光照下固化得到三层结构的聚合物光学膜。
所得聚合物光学膜的光致发光量子效率为68％。该聚合物光学膜在85℃温度、85％RH条件下放置100h，光致发光量子效率为50％。
与对比例3相比，虽然实施例1和实施例2所使用的量子点材料的初始量子点发光效率较其更低，但是制成聚合物光学膜后，其量子发光效率反而较其更高，主要原因是量子点的量子发光效率跟分散介质的折射率成正比，PVA的折射率较丙烯酸树脂高，导致最终分散在PVA膜中的量子点的发光效率高一些。此外，在85℃温度、85％RH的环境条件下，实施例1的量子点膜的量子点发光效率经过100h只衰减了1.5％，实施例2衰减了12％，而对比例3量子点膜的量子点发光效率衰减了18％。表明具有高结晶度的PVA高分子材料，具有非常优异的阻氧性能；而低结晶度的PVA同样具有一定的氧气阻隔性能，导致量子点发光效率衰减延缓。
与对比例3相比，实施例3的聚合物光学膜的初始光致发光量子效率较其高4个百分点，主要原因是量子点的量子发光效率跟分散介质的折射率成正比，PVA的折射率较丙烯酸树脂高，导致最终分散在PVA膜中的量子点的发光效率高一些。此外，实施例3的量子发光效率更稳定，样品在85℃温度、85％RH条件下100h仅衰减7个百分点，而对比例3的量子发光效率衰减了18个百分点，进一步证明结晶高分子能够提高量子点的稳定性。
实施例5：包含油相合成量子点+聚氧化乙烯(PEO)助剂+PVA的聚合物光学膜
首先，将80质量份PVA聚合物(Mowiol 24-88醇解度88.0mol％，聚合度3200，Sigma-Aldrich提供)、20质量份的PEO(1000000分子量，BASF提供)溶解在水中，温度90℃时溶解需要2.5h。然后用分散机将7.50质量份粒径为10μm的有机硅粒子(EL202A，涌奇材料提供)分散到上述PVA溶液中，分散速度1200rpm。最后，将0.25 质量份红色核壳结构光致发光量子点纳米晶体和1.0质量份绿色核壳结构光致发光量子点纳米晶体(均由天津Nanocomy提供)分散到上述PVA溶液中形成铸膜液，搅拌速度800rpm。该铸膜液含有75％质量份数的挥发水份。再将铸膜液在真空中脱气泡12h，随后在经过表面修饰的厚度为75μm的PET基膜上流延成型，再在70℃鼓风烘箱中干燥10min，随后在50℃真空干燥箱中干燥3h得到干膜(PVA/PET复合结构薄膜)。
然后，将另一张经过表面修饰后不易剥离的厚度同为75μm的PET基膜覆盖在PVA/PET膜上，使PVA量子点层夹在中间。然后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA与PET基膜之间，将上述制备的复合膜进行紫外曝光处理。使用能量为8W/cm 2的UV光曝光180s，使胶水固化，得到四层复合结构的聚合物光学膜。
所得聚合物光学膜的全线透光率为88％，雾度98％，初始光致发光量子效率为77％。样品在85℃温度、85％RH条件下放置100h，光致发光量子效率为72.6％。
与对比例3相比，实施例5的聚合物光学膜的初始量子点效率较其高9个百分点，主要原因是量子点的量子发光效率跟分散介质的折射率成正比，PVA的折射率较丙烯酸树脂高，导致最终分散在PVA膜中的量子点的发光效率高一些，此外，PEO可通过氢键作用与PVA结合，嵌入到PVA的非晶态链段中，形成更加致密的结构，使阻隔性提高。在85℃温度、85％RH的环境条件下，实施例5的聚合物光学膜的量子点发光效率100h衰减了4.4％，而对比例3中聚合物光学膜的量子点发光效率衰减了18％，证明与PEO溶液共混后的PVA高分子材料，具有更好的抗衰减性能。
实施例6：包含油相合成量子点+戊二醛助剂+PVA的聚合物光学膜
首先，将99.5质量份的PVA聚合物(Mowiol 24-88，醇解度88.0mol％，聚合度3200，Sigma-Aldrich提供)溶解在水中，温度90℃时溶解需要2.5h。然后用分散机将7.5质量份粒径为10μm的有机硅粒子(EL202A，涌奇材料提供)分散到上述PVA溶液中，分散速度1200rpm。之后，将0.25质量份红色核壳结构光致发光量子点纳米晶体和1.0质量份绿色核壳结构光致发光量子点纳米晶体(均由天津Nanocomy提供)分散到上述PVA溶液中形成铸膜液，搅拌速度800rpm。最后，将戊二醛盐酸混合液(包含5质量份浓度为10％的戊二醛水溶液和0.5质量份浓度为1.0mol/L的盐酸水溶液)分散到铸膜液中，搅拌速度500rpm。该铸膜液含有75％质量份数的挥发水份。再将铸膜液在真空中脱气泡12h，随后在经过表面修饰的厚度为75μm的PET基膜上流延成型，再在70℃鼓风烘箱中干燥10min，随后在50℃真空干燥箱中干燥3h得到干膜(PVA/PET复合结构薄膜)。
然后，将另一张经过表面修饰后不易剥离的厚度同为75μm的PET基膜覆盖在PVA/PET膜上，使PVA量子点层夹在中间。然后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA与PET基膜之间，将上述制备的复合膜进行紫外曝光处理。使用能量为8W/cm 2的UV光曝光180s，使胶水固化，得到四层复合结构的聚合物光学膜。
所得复合膜全线透光率为88％，雾度98％，初始光致发光量子效率为75％。样品在85℃温度、85％RH条件下放置100h，光致发光量子效率为69％。
与对比例3相比，实施例6的聚合物光学膜的初始量子点效率较其高7个百分点，主要原因是量子点的量子发光效率跟分散介质的折射率成正比，PVA的折射率较丙烯酸树脂高，导致最终分散在PVA膜中的量子点的发光效率高一些；此外，戊二醛在盐酸的催化下和PVA发生了缩醛反应，形成了适度的交联结构，使PVA的耐水性得到了提高，水汽难以渗透进PVA内部对量子点造成影响。在85℃温度、85％RH的环境条件下，实施例6的聚合物光学点的量子点发光效率100h衰减了6％，而对比例3的聚合物光学膜的量子点发光效率衰减了18％，证明添加了戊二醛的PVA高分子材料，具有更好的抗衰减性能。
实施例7：包含油相合成量子点+高结晶度PVA组合的聚合物光学膜
首先，将100质量份PVA聚合物(Mowiol 18-98，高结晶度，醇解度98.0mol％，聚合度2700，Sigma-Aldrich提供)和10质量份甘油溶解在二甲基亚砜中，温度90℃时溶解需要5h。其他条件同实施例1，即用分散机将7.5质量份粒径为10μm的有机硅粒子(EL202A，涌奇材料提供)分散到PVA溶液中，分散速度1200rpm。最后，将1.0质量份绿色核壳结构光致发光量子点纳米晶体和0.25质量份红色核壳结构光致发光量子点纳米晶体(油相量子点，南京大学邓正涛教授研发组提供，初始量子点发光效率70％)分散到PVA溶液中形成铸膜液，搅拌速度200rpm。该铸膜液含有75％质量份的挥发二甲基亚砜份。再将铸膜液在真空中脱气泡12h，随后在厚度为75μm的表面附着力大于40达因的PET基膜上流延成型，再在70℃鼓风烘箱中干燥10min，随后在50℃真空干燥箱中干燥3h得到干膜(PVA/PET复合结构薄膜)。
然后，将另一张经过表面修饰后不易剥离的厚度同为75μm的PET基膜覆盖在PVA/PET膜上，使PVA量子点层夹在中间。然后用滴管在中间挤涂UV光固化胶水，用压辊将胶水压平并均匀分布在PVA与PET基膜之间，将上述制备的复合膜进行紫外曝光处理。使用能量为8W/cm 2的UV光曝光180s，使胶水固化，得到四层复合结构，该结构如图1(a)所示。
所得复合膜全线透光率为85％，初始光致发光量子效率为70％。样品在85℃温度、85％RH条件下放置100h，全光线透光率为85％，雾度98％，光致发光量子效率为68.5％。
以上所述，仅是用来阐明本发明的个别实施案例而已，并非对本发明作任何形式上的限制。虽然本发明已以个别实施例揭露如上，然而并非用以限定本发明。任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，利用上述揭示的技术内容做出些许的更动或修饰将被视为等同变化的等效实施案例。但凡未脱离本发明技术方案内容，依据本发明的技术实质，在本发明的精神和原则之内，对以上实施案例所作的任何简单的修改、等同替换与改进等，均属于本发明技术方案的保护范围之内。

Claims (11)

  1. 抗氧化的量子点聚合物光学膜，其包含：
    两层基膜；
    夹在两层基膜中间的量子点膜；和
    一个或两个粘合剂层，所述粘合剂层位于所述基膜和所述量子点膜之间；
    其特征在于：
    所述量子点膜包含具有低氧气渗透率的聚合物、核壳结构的光致发光的量子点纳米晶体、和任选存在的光扩散剂。
  2. 如权利要求1所述的量子点聚合物光学膜，其中，所述具有低氧气渗透率的聚合物选自由乙烯-乙烯基醇共聚物、聚乙烯醇、
    Figure PCTCN2018071561-appb-100001
    树脂、液晶聚合物、聚偏二氯乙烯、聚丙烯酸、羟丙甲纤维素、聚胺类，例如聚二烯丙基二甲基氯化铵、双氰胺树脂、絮凝剂、两性高分子、聚丙烯酰胺、聚氧化乙烯及上述聚合物的改性衍生物组成的组中的一种或多种。
  3. 如权利要求1或2所述的量子点聚合物光学膜，其中，所述核壳结构的光致发光的量子点纳米晶体选自水相合成的量子点和经处理的油相合成的量子点。
  4. 如权利要求1-3任一项所述的量子点聚合物光学膜，其中，所述光致发光的量子点纳米晶体的固体含量相对于所述量子点膜的质量为0.01-10％。
  5. 如权利要求1-4任一项所述的量子点聚合物光学膜，其中，所述量子点膜的厚度为10μm-250μm。
  6. 如权利要求1-5任一项所述的量子点聚合物光学膜，其中，所述光扩散剂包括选自由二氧化硅、二氧化钛、改性有机硅化合物和聚合物胶体粒子组成的组中的一种或多种，其粒径在0.5-20μm之间。
  7. 如权利要求1-6任一项所述的量子点聚合物光学膜的制备方法，其中，使用水相合成的核壳结构的光致发光的量子点纳米晶体，所述方法包括：
    (1)用水或二甲基亚砜作为溶剂溶解具有低氧气渗透率的聚合物；
    (2)任选地，将光扩散剂分散入具有低氧气渗透率的聚合物溶液中；
    (3)将水相合成的核壳结构的光致发光的量子点纳米晶体分散到上述聚合物溶液中；
    (4)上述混合物经过脱泡工艺，形成铸膜液；
    (5)在基膜上流延，干燥成膜；
    (6)将另一基膜通过粘合剂层覆盖在上述形成的量子点膜上。
  8. 如权利要求7所述的制备方法，其中，如下进行步骤(6)，剥离掉步骤(5)中的基膜，通过粘合剂层分别将两层基膜覆盖在剥离后的量子点膜的相对面上。
  9. 如权利要求1-6任一项所述的量子点聚合物光学膜的制备方法，其中，使用油相合成的核壳结构的光致发光的量子点纳米晶体，所述方法包括：
    (1)将油相合成的核壳结构的光致发光的量子点纳米晶体进行预处理，所述预处理包括将量子点纳米晶体混合入疏水的聚合物中，制成量子点粉末，或者在量子点纳米晶体中加入选自抗氧化剂和阻氧材料中的一种或多种；
    (2)用水或二甲基亚砜作为溶剂溶解具有低氧气渗透率的聚合物；
    (3)任选地，将光扩散剂分散入具有低氧气渗透率的聚合物溶液中；
    (4)将上述经预处理的油相合成的核壳结构的光致发光的量子点纳米晶体分散到所溶聚合物中；
    (5)上述混合物经过脱泡工艺，形成铸膜液；
    (6)在基膜上流延，干燥成膜；
    (7)将另一基膜通过粘合剂层覆盖在上述形成的量子点膜上。
  10. 如权利要求9所述的制备方法，如下进行步骤(7)，剥离掉步骤(6)中的基膜，通过粘合剂层分别将两层基膜覆盖在剥离后的量子点膜的相对面上。
  11. 如权利要求1-6任一项所述的量子点聚合物光学膜的用途，其用于发光领域例如LEDs和显示屏。
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