Silver nano-cluster doped polyvinyl alcohol optical film as well as preparation method and application thereof
By doping silver nanoclusters into the polyvinyl alcohol optical film and preparing by casting method, the problem of insufficient performance of the polyvinyl alcohol optical film in the prior art is solved, and its mechanical properties and optical properties are improved.
Patent Information
- Application Number
- CN202311614082.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-29
- Publication Date
- 2025-05-30
AI Technical Summary
The prior art cannot optimize the performance of polyvinyl alcohol optical films from the field of molecular structure, resulting in insufficient mechanical and optical properties.
By doping silver nanoclusters into polyvinyl alcohol, a silver nanocluster doped polyvinyl alcohol optical film was prepared by casting method, and the polyvinyl alcohol was modified from the molecular structure level.
The silver nanocluster doped polyvinyl alcohol optical film has excellent mechanical properties and optical properties, which are specifically manifested in improving elongation of break, light transmittance and reducing haze.
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Figure BDA0004577602140000081 
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Abstract
Description
Technical Field
[0001] The present invention relates to a polyvinyl alcohol optical film, and specifically to a silver nanocluster-doped polyvinyl alcohol optical film, a preparation method thereof, and an application thereof. Background Art
[0002] The polyvinyl alcohol optical film has high transparency and good ductility, and is the core raw material of polarizers. It is mainly monopolized by Kuraray and Synthetic Chemical in Japan. It has good optical properties and has broad applications in fields such as light-emitting devices and light-emitting materials.
[0003] Currently, the preparation method of polyvinyl alcohol optical film mainly uses polyvinyl alcohol as the raw material, supplemented by additives such as plasticizers and surfactants to prepare a film-forming stock solution, which is cast or coated on a steel belt or roller, and obtained through processes such as drying.
[0004] The above method only optimizes the physical properties by using additives, only changes in the macroscopic field, and does not optimize the performance of polyvinyl alcohol from the molecular structure field to improve the product performance. Summary of the Invention
[0005] The purpose of the present invention is to overcome the problem that the existing technology cannot optimize the polyvinyl alcohol optical film from the molecular structure field, and provide a silver nanocluster-doped polyvinyl alcohol optical film, a preparation method thereof, and an application thereof. The silver nanocluster-doped polyvinyl alcohol optical film takes into account both excellent mechanical properties and optical properties.
[0006] To achieve the above purpose, in the first aspect of the present invention, a silver nanocluster-doped polyvinyl alcohol optical film is provided, wherein the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film include silver nanoclusters and polyvinyl alcohol.
[0007] In the second aspect of the present invention, a preparation method of a silver nanocluster-doped polyvinyl alcohol optical film is provided, wherein the preparation method includes: configuring a polyvinyl alcohol solution with polyvinyl alcohol, silver nanoclusters and water, and obtaining a silver nanocluster-doped polyvinyl alcohol optical film through a casting method.
[0008] In the third aspect of the present invention, a silver nanocluster-doped polyvinyl alcohol optical film prepared by the aforementioned preparation method is provided.
[0009] In the fourth aspect of the present invention, an application of the aforementioned silver nanocluster-doped polyvinyl alcohol optical film in the field of polarizers is provided.
[0010] Through the above technical solutions, the present invention has achieved the following beneficial effects:
[0011] The silver nanocluster-doped polyvinyl alcohol optical film in the present invention is doped and modified from the molecular structure of the polyvinyl alcohol optical film, so that the silver nanocluster-doped polyvinyl alcohol optical film can have both excellent mechanical properties and optical properties.
[0012] Furthermore, specific concentrations of silver nanoclusters and polyvinyl alcohol enable more thorough doping, further improving the mechanical and optical properties of the silver nanocluster-doped polyvinyl alcohol optical film. Detailed implementation manners
[0013] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.
[0014] In the first aspect of the present invention, a silver nanocluster-doped polyvinyl alcohol optical film is provided, wherein the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film include silver nanoclusters and polyvinyl alcohol.
[0015] In the present invention, the materials of the silver nanocluster-doped polyvinyl alcohol optical film include silver nanoclusters and polyvinyl alcohol. Modifying polyvinyl alcohol with silver nanoclusters at the molecular structure level enables the silver nanocluster-doped polyvinyl alcohol optical film to have excellent mechanical and optical properties.
[0016] In the present invention, silver nanoclusters are prepared by conventional preparation methods in the art. In a particularly preferred embodiment, silver nanoclusters are prepared by a photocatalytic reduction method. The specific synthesis method of the photocatalytic reduction method is as follows: Take 4.0 mL of carboxymethyl dextran with a concentration of 5.0×10 -3 mol / L and drop it into a weighing bottle with a specification of 50×30 mm, add 12 mL of water and a magnetic stirrer, place it on a magnetic stirrer and stir. While stirring, add 4 mL of silver ammonia solution with a concentration of 5.0×10 -3 mol / L, stir at room temperature for 10 min to make it fully mixed evenly. Place the evenly mixed solution open under a UVC-type ultraviolet lamp, stir and irradiate for 4 h while stirring. As the irradiation time increases, the color of the solution gradually changes from colorless and transparent to brownish yellow, and the target product silver nanoclusters are obtained.
[0017] According to the present invention, in the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film, the weight ratio of the silver nanoclusters to the polyvinyl alcohol is 1:1 - 12.
[0018] In the present invention, when the weight ratio of silver nanoclusters to polyvinyl alcohol satisfies the above range, the silver nanoclusters are more thoroughly dispersed in the polyvinyl alcohol, improving the compatibility between the two, and further improving the mechanical and optical properties of the silver nanocluster-doped polyvinyl alcohol optical film.
[0019] Further, in the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film, the weight ratio of the silver nanoclusters to the polyvinyl alcohol is 1:1 - 3.
[0020] According to the present invention, the thickness of the silver nanocluster-doped polyvinyl alcohol optical film is 50 - 70 μm, preferably 60 - 65 μm.
[0021] According to the present invention, the elongation at break of the silver nanocluster-doped polyvinyl alcohol optical film is 400 - 600%, the light transmittance is 90 - 95%, and the haze is 0.01 - 0.6%.
[0022] Further, the elongation at break of the silver nanocluster-doped polyvinyl alcohol optical film is 420 - 580%, the light transmittance is 90 - 93%, and the haze is 0.1 - 0.5%.
[0023] The second aspect of the present invention provides a method for preparing a silver nanocluster-doped polyvinyl alcohol optical film. The preparation method includes: configuring polyvinyl alcohol, silver nanoclusters, and water into a polyvinyl alcohol solution, and obtaining the silver nanocluster-doped polyvinyl alcohol optical film through a casting method.
[0024] In the present invention, by adding polyvinyl alcohol and silver nanoclusters simultaneously, at the molecular level, the silver nanoclusters can be fully dispersed in the polyvinyl alcohol, and the two are mutually blended, so that the prepared silver nanocluster-doped polyvinyl alcohol optical film has excellent mechanical properties and optical properties.
[0025] In the present invention, the casting method is a conventional casting method in the art. In a particularly preferred embodiment, the specific method of the casting method is: uniformly flowing the uniformly mixed polyvinyl alcohol solution onto a film-forming device through a casting device, and forming a film after drying. The drying temperature is 120 - 140 °C, and the drying time is 1 - 2 h.
[0026] According to the present invention, based on the polyvinyl alcohol solution, the content of the polyvinyl alcohol is 5 - 25 wt%, the content of the silver nanoclusters is 0.5 - 15 wt%, and the content of the water is 60 - 95 wt%.
[0027] In the present invention, when the contents of polyvinyl alcohol, silver nanoclusters, and water in the polyvinyl alcohol solution meet the above ranges, the doping degree of the silver nanoclusters is increased, the polyvinyl alcohol can be fully optimized, and further the mechanical properties and optical properties of the prepared silver nanocluster-doped polyvinyl alcohol optical film are improved.
[0028] Further, based on the polyvinyl alcohol solution, the content of the polyvinyl alcohol is 12 - 20 wt%, the content of the silver nanoclusters is 1 - 10 wt%, and the content of the water is 70 - 87 wt%.
[0029] The third aspect of the present invention provides a silver nanocluster-doped polyvinyl alcohol optical film prepared by the aforementioned preparation method.
[0030] The fourth aspect of the present invention provides an application of the aforementioned silver nanocluster-doped polyvinyl alcohol optical film in the field of polarizers.
[0031] The present invention will be described in detail below through examples.
[0032] The test method for the thickness of the silver nanocluster-doped polyvinyl alcohol optical film is as follows: Place the film flat on a platform and use a handheld contact thickness gauge for detection.
[0033] The test method for the elongation at break of the silver nanocluster-doped polyvinyl alcohol optical film: Clamp the film on the chuck of a tensile device, then soak it in water at 25 °C for 30 s, and then start stretching; elongation at break = (ΔL / L) × 100%, where ΔL is the relative increased length and L is the initial length.
[0034] The test method for the light transmittance of the silver nanocluster-doped polyvinyl alcohol optical film: Use a haze meter to test the light transmittance. Cut the film into a circular piece with a radius of 50 mm at normal temperature and pressure, and place it in the haze meter for testing. The test temperature is 93 °C.
[0035] The test method for the haze of the silver nanocluster-doped polyvinyl alcohol optical film: Use a haze meter to test the light transmittance. Cut the film into a circular piece of appropriate size at normal temperature and pressure, and place it in the haze meter for testing; haze = scattered light flux / transmitted light flux × 100%.
[0036] Polyvinyl alcohol (degree of polymerization is 1.7 million, degree of alcoholysis is 98%) is commercially available from Chongqing Chuanwei Chemical Co., Ltd., Sinopec Group.
[0037] The preparation method of silver nanoclusters is as follows: Take 4.0 mL of carboxymethyl dextran with a concentration of 5.0×10 -3 mol / L and drop it into a weighing bottle with a specification of 50×30 mm. Add 12 mL of water and a magnetic stirrer, place it on a magnetic stirrer and stir. While stirring, add 4 mL of silver ammonia solution with a concentration of 5.0×10 -3 mol / L. Stir at room temperature for 10 min to make it fully mixed. Place the well-mixed solution open under a UVC-type ultraviolet lamp, stir and irradiate for 4 h while stirring. As the irradiation time increases, the color of the solution gradually changes from colorless and transparent to brownish yellow, and the target product silver nanoclusters are obtained.
[0038] Example 1
[0039] At 25 °C, 12 g of polyvinyl alcohol, 1 g of silver nanoclusters, and 87 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of silver nanoclusters was 1 wt%, and the content of water was 87 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. A silver nanocluster-doped polyvinyl alcohol optical film A1 was prepared.
[0040] Among the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A1, the weight ratio of silver nanoclusters to polyvinyl alcohol was 1:12.
[0041] Example 2
[0042] At 25 °C, 12 g of polyvinyl alcohol, 2 g of silver nanoclusters, and 86 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of silver nanoclusters was 2 wt%, and the content of water was 86 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. A silver nanocluster-doped polyvinyl alcohol optical film A2 was prepared.
[0043] Among the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A2, the weight ratio of silver nanoclusters to polyvinyl alcohol was 1:6.
[0044] Example 3
[0045] At 25 °C, 12 g of polyvinyl alcohol, 3 g of silver nanoclusters, and 85 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of silver nanoclusters was 3 wt%, and the content of water was 85 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. A silver nanocluster-doped polyvinyl alcohol optical film A3 was prepared.
[0046] Among the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A3, the weight ratio of silver nanoclusters to polyvinyl alcohol was 1:4.
[0047] Example 4
[0048] At 25 °C, 12 g of polyvinyl alcohol, 4 g of silver nanoclusters, and 84 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of silver nanoclusters was 4 wt%, and the content of water was 84 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. A silver nanocluster-doped polyvinyl alcohol optical film A4 was prepared.
[0049] In the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A4, the weight ratio of silver nanoclusters to polyvinyl alcohol is 1:3.
[0050] Example 5
[0051] At 25°C, 12 g of polyvinyl alcohol, 5 g of silver nanoclusters, and 83 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol is 12 wt%, the content of silver nanoclusters is 5 wt%, and the content of water is 83 wt%. By the casting method, the drying temperature is 140°C and the drying time is 1 h. The silver nanocluster-doped polyvinyl alcohol optical film A5 was prepared.
[0052] In the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A5, the weight ratio of silver nanoclusters to polyvinyl alcohol is 1:2.4.
[0053] Example 6
[0054] At 25°C, 12 g of polyvinyl alcohol, 6 g of silver nanoclusters, and 82 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol is 12 wt%, the content of silver nanoclusters is 6 wt%, and the content of water is 82 wt%. By the casting method, the drying temperature is 140°C and the drying time is 1 h. The silver nanocluster-doped polyvinyl alcohol optical film A6 was prepared.
[0055] In the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A6, the weight ratio of silver nanoclusters to polyvinyl alcohol is 1:2.
[0056] Example 7
[0057] At 25°C, 12 g of polyvinyl alcohol, 8 g of silver nanoclusters, and 80 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol is 12 wt%, the content of silver nanoclusters is 8 wt%, and the content of water is 80 wt%. By the casting method, the drying temperature is 140°C and the drying time is 1 h. The silver nanocluster-doped polyvinyl alcohol optical film A7 was prepared.
[0058] In the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A7, the weight ratio of silver nanoclusters to polyvinyl alcohol is 1:1.5.
[0059] Example 8
[0060] At 25 °C, 12 g of polyvinyl alcohol, 10 g of silver nanoclusters, and 78 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of silver nanoclusters was 4 wt%, and the content of water was 84 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. The silver nanocluster-doped polyvinyl alcohol optical film A8 was prepared.
[0061] Among the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film A8, the weight ratio of silver nanoclusters to polyvinyl alcohol is 1:1.2.
[0062] Comparative Example 1
[0063] At 25 °C, 12 g of polyvinyl alcohol and 88 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of silver nanoclusters was 0, and the content of water was 88 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. The polyvinyl alcohol optical film D1 was prepared.
[0064] Among the materials constituting the polyvinyl alcohol optical film D1, the weight ratio of silver nanoclusters to polyvinyl alcohol is 0.
[0065] Comparative Example 2
[0066] At 25 °C, 12 g of polyvinyl alcohol, 8 g of gold nanoclusters, and 80 g of water were added to prepare 100 g of a polyvinyl alcohol solution. Based on the polyvinyl alcohol solution, the content of polyvinyl alcohol was 12 wt%, the content of gold nanoclusters was 8 wt%, and the content of water was 80 wt%. By the casting method, the drying temperature was 140 °C and the drying time was 1 h. The polyvinyl alcohol optical film D2 was prepared.
[0067] Among the materials constituting the polyvinyl alcohol optical film D2, the content ratio of gold nanoclusters to polyvinyl alcohol is 1:1.5.
[0068] The prepared silver nanocluster-doped polyvinyl alcohol optical films A1 - A8 and polyvinyl alcohol optical films D1 and D2 were tested, and the results are shown in Table 1.
[0069] Table 1
[0070]
[0071]
[0072] Comparing Example 7 with Comparative Example 2, it can be seen that when the silver nanoclusters are replaced with gold nanoclusters, the elongation at break of the prepared polyvinyl alcohol optical film decreases, the light transmittance decreases, and the haze increases; the specific silver nanoclusters in the present invention can blend with polyvinyl alcohol, so that the silver nanocluster-doped polyvinyl alcohol optical film can have both excellent mechanical properties and optical properties.
[0073] Comparing Examples 1-8, it can be seen that the concentration of the specific silver nanoclusters and polyvinyl alcohol in the polyvinyl alcohol optical film can further improve the mechanical properties and optical properties of the silver nanocluster-doped polyvinyl alcohol optical film.
[0074] Comparing the examples with Comparative Example 1, it can be seen that when no silver nanoclusters are added, the elongation at break of the polyvinyl alcohol optical film decreases and the light transmittance becomes worse.
[0075] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.
Claims
1. A silver nanocluster-doped polyvinyl alcohol optical film, characterized in that, the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film include silver nanoclusters and polyvinyl alcohol.
2. The silver nanocluster-doped polyvinyl alcohol optical film according to claim 1, wherein, in the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film, the weight ratio of the silver nanoclusters to the polyvinyl alcohol is 1:1 - 12.
3. The silver nanocluster-doped polyvinyl alcohol optical film according to claim 2, wherein, in the materials constituting the silver nanocluster-doped polyvinyl alcohol optical film, the weight ratio of the silver nanoclusters to the polyvinyl alcohol is 1:1 - 3.
4. The silver nanocluster-doped polyvinyl alcohol optical film according to any one of claims 1 - 3, wherein, the thickness of the silver nanocluster-doped polyvinyl alcohol optical film is 50 - 70 μm, preferably 60 - 65 μm.
5. The silver nanocluster-doped polyvinyl alcohol optical film according to any one of claims 1 - 4, wherein, the elongation at break of the silver nanocluster-doped polyvinyl alcohol optical film is 400 - 600%, the light transmittance is 90 - 95%, and the haze is 0.01 - 0.6%; preferably, the elongation at break of the silver nanocluster-doped polyvinyl alcohol optical film is 420 - 580%, the light transmittance is 90 - 93%, and the haze is 0.1 - 0.5%.
6. A preparation method of a silver nanocluster-doped polyvinyl alcohol optical film, characterized in that, the preparation method includes: configuring polyvinyl alcohol, silver nanoclusters and water into a polyvinyl alcohol solution, and obtaining the silver nanocluster-doped polyvinyl alcohol optical film by a casting method.
7. The preparation method according to claim 6, wherein, based on the polyvinyl alcohol solution, the content of polyvinyl alcohol is 5 - 25 wt%, the content of silver nanoclusters is 0.5 - 15 wt%, and the content of water is 60 - 95 wt%.
8. The preparation method according to claim 7, wherein, based on the polyvinyl alcohol solution, the content of polyvinyl alcohol is 12 - 20 wt%, the content of silver nanoclusters is 1 - 10 wt%, and the content of water is 70 - 87 wt%.
9. A silver nanocluster-doped polyvinyl alcohol optical film prepared by the preparation method according to any one of claims 6 - 8.
10. Application of the silver nanocluster-doped polyvinyl alcohol optical film according to any one of claims 1 - 5 or claim 9 in the field of polarizing films.