POK quantum dot diffusion plate and preparation method thereof

Abstract

The invention discloses a POK quantum dot diffusion plate and a preparation method thereof, wherein the diffusion plate comprises the following components in parts by mass: 85-95 parts of POK resin, 0.8-2.4 parts of quantum dots, 1-3 parts of organosilicon light diffusers, 0.15-0.45 parts of antioxidants, 1-5 parts of mineral oils, 0.6-1.2 parts of light stabilizers, 0.4-0.8 parts of ultraviolet absorbers, 0.05-0.15 parts of brighteners, and 1-2 parts of dodecylamine. The product has the advantages of stable luminescence, good toughness, high light transmittance, and not easy to age and turn yellow, while maintaining high water and oxygen barrier properties and luminescence efficiency. It has good comprehensive performance and strong market competitiveness.

Description

Technical Field

[0001] The present invention relates to the technical field of diffusion plates, and specifically to a POK quantum dot diffusion plate and a preparation method thereof. Background Art

[0002] Quantum dots are a type of nano-scale semiconductor. By applying a certain electric field or light pressure to this nano-semiconductor material, they will emit light of a specific frequency. Existing technologies often combine quantum dot technology with light diffusers to make quantum dot diffusers. However, since quantum dots are very sensitive to heat, oxygen and water, there are the following difficulties that need to be overcome in the preparation process: first, how to evenly disperse the quantum dots in the polymer masterbatch; second, the quantum yield of quantum dots will decrease during high-temperature granulation or extrusion processes, which will in turn affect the luminous efficiency and stability.

[0003] Aliphatic polyketone (POK) resin is a high-performance thermoplastic polymer. It is a linear crystalline polymer obtained by alternating copolymerization of carbon monoxide and ethylene. Since POK material has a carbonyl group on the main chain of the molecule and has high stability, POK material generally has excellent hydrolysis resistance, high temperature resistance and chemical resistance, and can be used to make light diffuser plates. However, the disadvantages of POK light diffuser plates are also obvious, such as poor transparency, poor surface scratch resistance, poor weather resistance, easy yellowing, and poor solvent resistance.

[0004] Simply adding POK resin to the quantum dot diffusion plate will still cause brightness decay and poor luminous efficiency as the quantum dots become inactive, because the quantum dots cannot be stably and evenly dispersed in the POK resin. Therefore, how to combine POK with quantum dots to obtain a POK quantum dot diffusion plate with good water and oxygen barrier properties, high luminous efficiency, stable luminescence, good toughness, high light transmittance, and not easy to age and turn yellow is a topic worth studying, but no reports on this have been seen so far. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a POK quantum dot diffusion plate, which includes the following components in parts by mass: 85-95 parts of POK resin, 0.8-2.4 parts of quantum dots, 1-3 parts of silicone light diffusers, 0.15-0.45 parts of antioxidants, 1-5 parts of mineral oils, 0.6-1.2 parts of light stabilizers, 0.4-0.8 parts of ultraviolet absorbers, 0.05-0.15 parts of brighteners, and 1-2 parts of dodecylamine.

[0006] Furthermore, the quantum dots are oil-soluble CdSe / ZnS quantum dots.

[0007] Furthermore, the organic silicon light diffuser is Japan Shin-Etsu KMP-590.

[0008] Furthermore, the antioxidant is at least one of antioxidant 1024 , antioxidant 1010 or antioxidant 1076 .

[0009] Furthermore, the mineral oil is silicone oil or liquid paraffin.

[0010] Furthermore, the light stabilizer is any one or more selected from the group consisting of light stabilizer 622, light stabilizer 770, and light stabilizer 944.

[0011] Furthermore, the ultraviolet absorber is selected from one or more of the ultraviolet absorbers UV-327, UV-329, and UV-531.

[0012] Furthermore, the whitening agent is fluorescent whitening agent CBS-127.

[0013] The present invention also provides a method for preparing a POK quantum dot diffusion plate, comprising the following steps:

[0014] Add quantum dots and dodecylamine according to the above mass fractions into mineral oil and stir, slowly heat to 220° C. under oil bath conditions and maintain for 5 min, stop heating, continue stirring and cool to obtain mixture a;

[0015] The POK resin, the silicone light diffuser, the antioxidant, the light stabilizer, the ultraviolet absorber, the brightener and the mixture a are uniformly mixed according to the above mass fractions, and then put into a single screw extruder for heating and melting, and the single screw extruder is used for extrusion and embossing to obtain a finished product;

[0016] Among them, the temperatures of each zone of the single-screw extruder are: zone one temperature is 180~190℃, zone two temperature is 190~200℃, zone three temperature is 210~220℃, zone four temperature is 210~220℃, zone five temperature is 225~235℃, zone six temperature is 215~225℃, zone seven temperature is 210~220℃, and the die head temperature is 205~215℃.

[0017] The beneficial effect is that the present application provides a POK quantum dot diffusion plate, which has the advantages of stable luminescence, good toughness, high light transmittance, and not easy to age and turn yellow, while maintaining high water and oxygen barrier properties and luminous efficiency. The oil-soluble CdSe / ZnS quantum dots selected in the present application contain n-octyl mercaptan ligands on the surface, which are compatible with the POK resin, and the quantum dots are evenly dispersed in the POK resin; at the same time, the addition of dodecylamine can not only improve the surface polarity of the oil-soluble CdSe / ZnS quantum dots, but also form covalent bonds with the POK resin matrix under high temperature and high pressure, so that the material is formed inside. Cross-linked structure, quantum dots are stable in the POK resin matrix, so the quantum dot clusters are small, the product has high light transmittance, stable luminescence, reduced light scattering, quantum dots can be more effectively excited, thereby obtaining higher fluorescence intensity, high luminescence efficiency, and the cross-linked structure also increases the overall density of the product, making it difficult for water vapor and oxygen molecules to penetrate, and the product has better water and oxygen barrier properties; in addition, because the quantum dots are evenly dispersed in the POK resin and can also be stabilized in the POK resin matrix, the contact area between the quantum dots and the matrix is ​​larger, the product has better stability and toughness, and is convenient for later processing and use. This product combines the advantages of quantum dot diffusion plate and POK resin, and is more competitive in the market. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below in conjunction with specific embodiments so that those skilled in the art can understand the present invention more clearly.

[0019] The following embodiments are only used to illustrate the present invention, but are not limited to the scope of the present invention. Based on the specific embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work belong to the protection scope of the present invention.

[0020] In the examples of the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art; in the examples of the present invention, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art.

[0021] Source of raw materials:

[0022] The POK resin was model M330A from Hyosung Group, Korea;

[0023] Oil-soluble CdSe / ZnS quantum dots were purchased from Xingzi (Shanghai) New Materials;

[0024] InP / ZnS quantum dots were purchased from Xingzi (Shanghai) New Materials;

[0025] Organic silicon light diffuser KMP-590, purchased from Shin-Etsu, Japan;

[0026] Antioxidants were purchased from Shandong Xuxiang Chemical Co., Ltd.

[0027] Silicone oil was purchased from Jinan Xuchuang Chemical Technology Co., Ltd.

[0028] Liquid paraffin was purchased from Hefeng New Energy Co., Ltd.;

[0029] Light stabilizer, purchased from Shanghai Tiandui New Materials Co., Ltd.;

[0030] Ultraviolet absorber, purchased from Jinan Xiangfeng Weiye Chemical Co., Ltd.;

[0031] Fluorescent brightener CBS-127, purchased from Guangzhou Yuanda New Materials Co., Ltd.;

[0032] Dodecylamine was purchased from Guangzhou Ruishi Biotechnology Co., Ltd.

[0033] Example 1

[0034] This embodiment provides a POK quantum dot diffusion plate, which includes the following components in parts by mass: 90 parts of POK resin, 1.6 parts of quantum dots, 2 parts of silicone light diffuser, 0.3 parts of antioxidant, 3 parts of mineral oil, 0.9 parts of light stabilizer, 0.6 parts of ultraviolet absorber, 0.1 parts of brightener, and 1.5 parts of dodecylamine;

[0035] The POK resin is model M330A of the Korean Hyosung Group, the melt flow rate of the POK resin at 240°C / 2.16kg is 60g / 10min, the quantum dots are oil-soluble CdSe / ZnS quantum dots, the antioxidant is antioxidant 1024, the mineral oil is liquid paraffin, the light stabilizer is light stabilizer 770, the ultraviolet absorber is ultraviolet absorber UV-327, and the brightener is fluorescent brightener CBS-127;

[0036] The POK quantum dot diffusion plate is prepared according to the following steps:

[0037] Add quantum dots and dodecylamine according to the above mass fractions into mineral oil and stir, slowly heat to 220° C. under oil bath conditions and maintain for 5 min, stop heating, continue stirring and cool to obtain mixture a;

[0038] The POK resin, the silicone light diffuser, the antioxidant, the light stabilizer, the ultraviolet absorber, the brightener and the mixture a are uniformly mixed according to the above mass fractions, and then put into a single screw extruder for heating and melting, and the single screw extruder is used for extrusion and embossing to obtain a finished product;

[0039] Among them, the temperatures of each zone of the single-screw extruder are: zone 1 temperature is 185°C, zone 2 temperature is 195°C, zone 3 temperature is 215°C, zone 4 temperature is 215°C, zone 5 temperature is 230°C, zone 6 temperature is 220°C, zone 7 temperature is 215°C, and the die head temperature is 210°C.

[0040] Example 2

[0041] Different from Example 1, the POK quantum dot diffusion plate of this embodiment includes the following components in parts by mass: 95 parts of POK resin, 0.8 parts of quantum dots, 1 part of silicone light diffuser, 0.15 parts of antioxidant, 1 part of mineral oil, 0.6 parts of light stabilizer, 0.4 parts of ultraviolet absorber, 0.05 parts of brightener, and 1 part of dodecylamine; wherein the antioxidant is antioxidant 1010, the mineral oil is silicone oil, the light stabilizer is light stabilizer 944, and the ultraviolet absorber is ultraviolet absorber UV-329; in addition, during the preparation process, the temperatures of each zone of the single-screw extruder are: the temperature of zone 1 is 180°C, the temperature of zone 2 is 190°C, the temperature of zone 3 is 210°C, the temperature of zone 4 is 210°C, the temperature of zone 5 is 225°C, the temperature of zone 6 is 215°C, the temperature of zone 7 is 210°C, and the die head temperature is 205°C.

[0042] Example 3

[0043] Different from Example 1, the POK quantum dot diffusion plate of this embodiment includes the following components in parts by mass: 85 parts of POK resin, 2.4 parts of quantum dots, 3 parts of silicone light diffuser, 0.45 parts of antioxidant, 5 parts of mineral oil, 1.2 parts of light stabilizer, 0.8 parts of ultraviolet absorber, 0.15 parts of brightener, and 2 parts of dodecylamine; wherein the antioxidant is antioxidant 1076, the mineral oil is liquid paraffin, the light stabilizer is light stabilizer 622, and the ultraviolet absorber is ultraviolet absorber UV-531; in addition, during the preparation process, the temperatures of each zone of the single-screw extruder are: the temperature of zone 1 is 190°C, the temperature of zone 2 is 200°C, the temperature of zone 3 is 220°C, the temperature of zone 4 is 220°C, the temperature of zone 5 is 235°C, the temperature of zone 6 is 225°C, the temperature of zone 7 is 220°C, and the die head temperature is 215°C.

[0044] Comparative Example 1

[0045] The difference between this comparative example and Example 1 is that 90 parts of GPPS replace 100 parts of POK resin in Example 1, and the other components and experimental steps are the same as those in Example 1.

[0046] Comparative Example 2

[0047] The difference between the comparative example and the example one is that the amount of POK resin is increased from 90 parts to 91.5 parts, and dodecylamine is not added. The other components and experimental steps are the same as those of the example one.

[0048] Comparative Example 3

[0049] The difference between this comparative example and Example 1 is that the amount of POK resin is increased from 90 parts to 93 parts, and mineral oil liquid paraffin is not added. The other components and experimental steps are the same as those of Example 1.

[0050] Comparative Example 4

[0051] The difference between this comparative example and Example 1 is that 1.6 parts of InP / ZnS quantum dots are used to replace 1.6 parts of oil-soluble CdSe / ZnS quantum dots in Example 1, and the other components and experimental steps are the same as those in Example 1.

[0052] Comparative Example 5

[0053] The difference between this comparative example and Example 1 is that the POK quantum dot diffusion plate is prepared according to the following steps: all components are directly put into a single-screw extruder for heating and melting, and the finished product is extruded and embossed by the single-screw extruder; the temperature of each zone of the single-screw extruder is the same as that in Example 1.

[0054] Comparative Example 6

[0055] This comparative example is a quantum dot diffusion plate produced by Nantong Chuang Yida New Materials Co., Ltd., product model CPQ18B.

[0056] The diffuser plates prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were tested.

[0057] Test method:

[0058] Light transmittance and haze are tested according to ASTM D1003 standard;

[0059] The center brightness and average brightness are tested according to GY / T 326-2019 standard;

[0060] Water barrier performance is usually characterized by water vapor transmission rate (GB / T 1037), which is usually measured at 38℃ / 90RH to measure the mass of water vapor permeating through a unit area of ​​the film, in units of g / (m 2 24h);

[0061] The oxygen barrier performance is characterized by oxygen transmission rate (GB / T 1038), which measures and calculates the volume of oxygen that passes through the sample within 24 hours, in cm 3 / (m 2 ·24h·0.1MPa);

[0062] Brightness retention rate test method: Place the quantum dot diffusion plate at 60°C and 90% RH humidity for 1000 hours, detect the brightness values ​​before and after placement, and calculate the brightness retention rate, brightness retention rate = (brightness value after aging / brightness value before aging) * 100%;

[0063] Brightness and color point detection method: Place the quantum dot diffusion plate under the blue light LED module, and use the CA-310 color analyzer to test the center point brightness, color point X, and color point Y. The current is fixed at 174mA and the voltage is fixed at 8.3V.

[0064] The test results are shown in Table 1.

[0065] From the experimental data in Table 1, the POK quantum dot diffusion plates prepared in each embodiment of the present application have a transmittance of more than 60%, a haze of more than 90%, a central brightness and an average brightness of more than 2000, and a brightness retention rate of more than 90%, indicating that each embodiment has high luminous efficiency, good transmittance, and is not easy to age and turn yellow; the color coordinate X offset and the color coordinate Y offset are excellent, indicating that the luminescence of each embodiment is stable; the water vapor transmission rate is less than 0.5g / (m 2 ·24h), oxygen permeability coefficient is less than 0.6cm 3 / (m 2 ·24h·0.1MPa), indicating that each embodiment has high water and oxygen barrier properties; the impact strength is greater than 300Kg / cm 2 , indicating that the diffusion plates prepared in each embodiment have high impact resistance and good toughness; after a careful analysis of the experimental data of the three groups of embodiments, it is found that the various performance indicators of Example 1 are better than those of Examples 2 and 3, indicating that the ratio between the components has an impact on various performances. Therefore, in actual production applications, it is necessary to flexibly adjust the ratio of each group according to the situation to obtain a product with excellent comprehensive performance.

[0066] Table 1 Diffuser plate performance test results

[0067]

[0068] Continuing to compare and analyze the data of Example 1 with the six groups of comparative examples, it was found that the experimental data of Example 1 were also better than those of the comparative examples. After replacing the POK resin with GPPS in Comparative Example 1, the compatibility between the quantum dots and GPPS was poor, resulting in quantum dot clusters, which led to the poor light transmittance, unstable luminescence, and poor water and oxygen barrier properties of the comparative example product compared with the product of Example 1; since no dodecylamine was added to Comparative Example 2, a cross-linked structure could not be formed inside the product, and the quantum dots could not be stabilized in the POK resin matrix, resulting in unstable luminescence, low luminescence efficiency, and low water and oxygen barrier properties of the product; Mineral oil liquid paraffin was not added to Comparative Example 3, the quantum dots were unevenly dispersed, and without mineral oil liquid paraffin as a medium, dodecylamine could not improve the surface polarity of the oil-soluble CdSe / ZnS quantum dots, resulting in the compatibility of the quantum dots with the POK resin not being as good as in Example 1, and the product Poor transmittance and low luminous efficiency; After replacing the oil-soluble CdSe / ZnS quantum dots with InP / ZnS quantum dots in Comparative Example 4, the quantum dots and POK resin also have the problem of poor compatibility, and the cross-linked structure cannot be formed inside the product, the quantum dots cannot be stabilized in the POK resin matrix, and the quantum dots are easily deactivated, resulting in unstable luminescence of the product, low luminous efficiency, poor water and oxygen barrier, and no toughness; Comparative Example 5 directly puts all the components into a single-screw extruder for heating and melting, lacks the previous experimental steps, resulting in the inability to improve the surface polarity of the oil-soluble CdSe / ZnS quantum dots, and the oil-soluble CdSe / ZnS quantum dots and dodecylamine cannot be evenly dispersed in the system. Even after heating and melting, a cross-linked structure with uniform density cannot be formed, resulting in an unbalanced overall product structure, excessive color coordinate X offset and color coordinate Y offset, and unstable products. From the experimental results, all indicators of Example 1 are better than the mass-produced sample (CPQ18B) on the market, with better comprehensive performance and more market competitiveness.

[0069] In summary, the POK quantum dot diffusion plate developed in this application, while maintaining high water and oxygen barrier properties and luminous efficiency, also has the advantages of stable luminescence, good toughness, high light transmittance, and not easy to age and turn yellow. It combines the advantages of quantum dot diffusion plate and POK resin and has broad application prospects.

[0070] The above is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A POK quantum dot diffusion plate, characterized in that: The composition includes the following components in parts by mass: 85-95 parts of POK resin, 0.8-2.4 parts of oil-soluble CdSe / ZnS quantum dots, 1-3 parts of silicone light diffuser, 0.15-0.45 parts of antioxidant, 1-5 parts of mineral oil, 0.6-1.2 parts of light stabilizer, 0.4-0.8 parts of ultraviolet absorber, 0.05-0.15 parts of brightener, and 1-2 parts of dodecylamine; The preparation of the POK quantum dot diffusion plate comprises the following steps: adding the oil-soluble CdSe / ZnS quantum dots and dodecylamine to mineral oil according to the above mass fractions and stirring, slowly heating to 220° C. under oil bath conditions and maintaining for 5 minutes, stopping heating, continuing stirring and cooling to obtain a mixture a; The POK resin, the silicone light diffuser, the antioxidant, the light stabilizer, the ultraviolet absorber, the brightener and the mixture a are mixed evenly according to the above mass fractions, and then put into a single screw extruder to heat and melt, and the single screw extruder is used to extrude and emboss to obtain a finished product; Among them, the temperatures of each zone of the single-screw extruder are: zone one temperature is 180~190℃, zone two temperature is 190~200℃, zone three temperature is 210~220℃, zone four temperature is 210~220℃, zone five temperature is 225~235℃, zone six temperature is 215~225℃, zone seven temperature is 210~220℃, and the die head temperature is 205~215℃.

2. The POK quantum dot diffusion plate according to claim 1, characterized in that: The organosilicon light diffuser is Japan Shin-Etsu KMP-590.

3. The POK quantum dot diffusion plate according to claim 1, characterized in that: The antioxidant is at least one of antioxidant 1024, antioxidant 1010 or antioxidant 1076.

4. The POK quantum dot diffusion plate according to claim 1, characterized in that: The mineral oil is silicone oil or liquid paraffin.

5. The POK quantum dot diffusion plate according to claim 1, characterized in that: The light stabilizer is any one or more selected from the group consisting of light stabilizer 622, light stabilizer 770, and light stabilizer 944.

6. The POK quantum dot diffusion plate according to claim 1, characterized in that: The ultraviolet absorber is selected from one or more of the ultraviolet absorbers UV-327, UV-329, and UV-531.

7. The POK quantum dot diffusion plate according to claim 1, characterized in that: The whitening agent is fluorescent whitening agent CBS-127.

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