A method for preparing in-situ grown nano-silver anti-ultraviolet polymer composite film

Abstract

The invention discloses a preparation method of an in-situ grown nano silver anti-ultraviolet polymer composite film, belonging to the technical field of nano particles and polymer composite films, comprising the following steps: by weight, 5-20% polyvinyl pyrrolidone, 70-88% anhydrous ethanol, 0.5-2% silver salt, 0-4.5% reducing agent and 1.5-5% silane coupling agent are uniformly mixed, reacted at 20-80 DEG C for 2-24 hours, coated on a glass sheet or a spectacle lens, and dried at room temperature to form a film; the invention can be used for a one-time coating of spectacles or glass, can protect eyes from ultraviolet damage in an outdoor environment with strong sunlight, and can also be used in scenes where ultraviolet rays need to be blocked.

Description

Technical Field

[0001] The present application relates to a method for preparing an in-situ grown nano silver anti-ultraviolet polymer composite film, belonging to the technical field of nano particle and polymer composite film. Background Art

[0002] In an environment with strong sunlight, especially the ultraviolet rays, it can cause damage to people's eyes. For this reason, people with good eyesight can directly wear sunglasses, while people with poor eyesight who need to wear glasses to adjust their vision need to use special glasses such as photochromic glasses to protect their eyes from ultraviolet damage. Photochromic glasses are glasses made of color-changing materials, which change their color under the irradiation of light of appropriate wavelengths and restore their original color when the light source is removed. The materials of color-changing glasses are divided into color-changing glass or photochromic resin. Color-changing glass is made by adding photochromic materials to glass raw materials. This material has two different molecular or electronic structure states and two different absorption coefficients in the visible light region. Under the action of light, it can change from one structure to another, resulting in a reversible change in color.

[0003] Commonly used photochromic glass is usually silver bromide photochromic glass. When exposed to sunlight or ultraviolet rays, the silver bromide in it decomposes to produce silver atoms that can attract visible light. When the silver atoms gather to a certain number, most of the light shining on the glass is absorbed, and the originally colorless and transparent glass will turn gray and black. When the color-changed glass is placed in a dark place, under the catalysis of copper oxide, silver and bromine react to form silver bromide. Because silver ions do not absorb visible light, the glass will become colorless and transparent again. This kind of photochromic glass glasses are not easy to fatigue, and they still do not fail after experiencing more than 300,000 changes in light and dark. However, photochromic glass is heavy, fragile, and fades slowly. It is not suitable for environments with fast changes in light. It also has high manufacturing costs and is difficult to process.

[0004] Photochromic resin lenses are divided into film-layer photochromic lenses and base-layer photochromic lenses. Film-layer photochromic lenses are made by coating the surface of the lens with photochromic materials. They have the advantages of fast color change speed and uniform color, avoiding the problem of different color depths caused by uneven lens thickness. However, the color-changing film layer is easily damaged in daily life, resulting in a short service life. Base-layer photochromic lenses are obtained by melting photochromic powder into the lens monomer in the initial stage of production. The process is simple, the cost is low, the service life is long, and the durability is high. However, their shortcoming is that they cannot be used in high-power lenses. The center thickness and edge thickness of high-power lenses differ greatly. After the high-power lenses using base-layer photochromic technology change color, the center point color is light and the edge color is dark, which will form "panda eyes".

[0005] In addition, photochromic glasses are difficult to change color due to the obstruction of the car windows while driving, and strong light will dazzle the eyes, causing driving hazards. They cannot play a role in protecting the eyes and ensuring driving safety. Summary of the invention

[0006] In view of the problems that glass photochromic lenses on the current market are heavy, fragile, slow to fade and expensive, while resin photochromic lenses have poor durability or cannot be used in high-intensity lenses and are difficult to change color in cars, the first aspect of the present invention aims to provide a composite film material with excellent UV resistance.

[0007] The technical solution adopted by the present invention is as follows:

[0008] An in-situ grown nano silver anti-ultraviolet polymer composite film, characterized by comprising the following components by weight percentage:

[0009]

[0010] The present invention also provides a method for preparing an in-situ grown nano silver anti-ultraviolet polymer composite film, which is characterized in that it comprises the following steps: by weight, 5-20% polyvinyl pyrrolidone, 70-88% ethanol, 0.5-2% silver salt, 0.5-4.5% reducing agent, and 1.5-5% silane coupling agent are uniformly mixed, reacted at 20-80° C. for 2-24 hours, coated on a glass sheet or a spectacle lens, and dried at room temperature to form a film.

[0011] Further settings are:

[0012] The ethanol is anhydrous ethanol.

[0013] The molecular weight of the polyvinyl pyrrolidone is 8000-500000.

[0014] The silver salt is silver nitrate, silver acetate or silver sulfate.

[0015] The reducing agent is vitamin C, glucose or tannic acid.

[0016] The silane coupling agent is γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxy(ethyl)silane, γ-methacryloxypropyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy)silane, γ-mercaptopropyl triethoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane or N-β-(aminoethyl)-γ-aminopropyl methyldimethoxysilane.

[0017] The reaction temperature is 50-80°C, and the reaction time is 12-24 hours, and the reaction temperature is particularly preferably 50°C, and the reaction time is 12 hours.

[0018] The present invention also provides an application of the above-mentioned in-situ grown nano silver anti-ultraviolet polymer composite film in the preparation of photochromic glasses, which is characterized in that the mixed solution after the reaction is directly applied to the glasses lens to form a film.

[0019] The beneficial effects of the present invention are as follows:

[0020] (1) The present invention first dissolves polyvinyl pyrrolidone in ethanol, then adds silver salt, coupling agent, and reducing agent, stirs and mixes evenly, and reacts at a certain temperature and time to obtain a polyvinyl pyrrolidone solution based on in-situ growth of nanosilver. The solution is easy to form a film at room temperature, has anti-ultraviolet properties, and can be wiped off with a wet wipe or washed with water. It can be used for one-time coating of glasses or glass, can protect eyes from ultraviolet damage in outdoor environments with strong sunlight, and can also be used in scenes where ultraviolet rays need to be blocked.

[0021] (2) The manufacturing process of the present invention is simple, the operation is convenient and controllable, it is environmentally friendly and pollution-free, it has low cost, and it can effectively protect the eyes from ultraviolet rays, which is good news for people who wear glasses. It can also be used in fields that require ultraviolet resistance.

[0022] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several changes and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The following are scanning electron microscope photos of the film prepared in Example 1 and a pure PVP film.

[0024] Figure 2 Elemental analysis results of the film prepared in Example 1 and pure PVP film.

[0025] Figure 3 The ultraviolet absorption curve of the film prepared in Example 1 (A is the absorbance curve, B is the transmittance curve)

[0026] Figure 4 The glass sheet covered with the film of Example 1 was tested with an ultraviolet sensor card before and after ultraviolet irradiation.

[0027] Figure 5 The ultraviolet absorption curve of the film prepared in Example 2 (A is the absorbance curve, B is the transmittance curve)

[0028] Figure 6 The ultraviolet absorption curve of the film prepared in Example 3 (A is the absorbance curve, B is the transmittance curve)

[0029] Figure 7 The ultraviolet absorption curve of the film prepared in Example 4 (A is the absorbance curve, B is the transmittance curve)

[0030] Figure 8 The ultraviolet absorption curve of the pure PVP film prepared in Comparative Example 1 (A is the absorbance curve, B is the transmittance curve)

[0031] Fig. 9 The glass sheet covered with the pure PVP film of Comparative Example 1 was tested with an ultraviolet sensor card before and after ultraviolet irradiation. DETAILED DESCRIPTION

[0032] Example 1

[0033] A method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film comprises the following components in parts by mass:

[0034]

[0035] The preparation method is as follows: 10 g of polyvinyl pyrrolidone, 85 g of anhydrous ethanol, 2 g of silver nitrate, 1.5 g of tannic acid, and 1.5 g of γ-glycidyloxypropyltrimethoxysilane are mixed evenly, reacted at 50° C. for 12 hours, then coated on a glass sheet, and dried at room temperature to form a film, thereby obtaining an in-situ grown nanosilver anti-ultraviolet polymer composite film, which is marked as PVP2177-4.

[0036] Product Confirmation:

[0037] The PVP2177-4 film prepared in Example 1 of the present invention and the pure PVP film (preparation method see Comparative Example 1) were observed by scanning electron microscope respectively. Figure 1 As shown: Figure 1 The surface morphology of the pure PVP film and the film prepared in Example 1 is shown by scanning electron microscopy. By comparison, it is found that although the surface of the pure PVP film is not smooth, there are no obvious particles, while a large number of particles are present on the surface of the composite film prepared in Example 1, and the particle size is tens of nanometers, indicating that nanoparticles grow in Example 1. Further elemental analysis was performed on the local area of ​​the sample (such as Figure 2 As shown), it was found that silver was detected in the film sample prepared in Example 1, but not in the pure PVP film, thus proving that silver was successfully grown in situ in the PVP matrix.

[0038] Performance Test:

[0039] The in-situ grown nanosilver anti-ultraviolet polymer composite film prepared in Example 1 was subjected to ultraviolet absorption performance test and ultraviolet resistance test.

[0040] UV resistance test: UV resistance is tested by UV sensor card. The UV sensor card is coated with phosphor coating in the sensing area and has the function of color change to measure UV intensity. It is used to sense UV light with a wavelength of 200-400nm and can sense up to 3000uW / cm 2 The intensity of ultraviolet light can be measured by measuring the color changes of the test layer under UV light or sunlight. Figure 4 As shown, the example is placed on an ultraviolet sensor card and irradiated with a UV lamp for a certain period of time, then the example is removed and the changes in the area covered with the example and the area not covered with the example are observed.

[0041] Test results:

[0042] Figure 3 is the ultraviolet absorption curve of the film prepared in Example 1 (A is the absorbance curve, B is the transmittance curve), from Figure 3 It can be seen that there is strong absorption in the ultraviolet region of 320-580 nanometers. In order to better detect the anti-ultraviolet properties. Figure 4 The ultraviolet sensor card is used to test the situation before and after ultraviolet light irradiation. It can be found that the glass piece coated with the film of Example 1 is brown and transparent. After irradiation with ultraviolet light, the ultraviolet sensor card does not change color, while the part not coated with the film of Example 1 changes color after irradiation with ultraviolet light, indicating that the film of Example 1 has an anti-ultraviolet effect.

[0043] Example 2

[0044] A method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film, the preparation method is as follows:

[0045] 6 g of polyvinyl pyrrolidone, 87 g of anhydrous ethanol, 0.5 g of silver acetate, 1.5 g of tannic acid, and 5 g of γ-methacryloxypropyltrimethoxysilane were mixed evenly, reacted at 20°C for 24 hours, coated on a glass slide, and dried at room temperature to form a film.

[0046] Performance test: The ultraviolet absorption performance of the film prepared in Example 2 was tested. Figure 5 As shown: It can be seen that there is absorption in the ultraviolet region of 320-580 nanometers.

[0047] Example 3

[0048] A method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film, the preparation method is as follows:

[0049] 20g of polyvinyl pyrrolidone, 70g of anhydrous ethanol, 1g of silver nitrate, 4.5g of glucose, and 4.5g of vinyl tri(β-methoxyethoxy)silane were mixed evenly, reacted at 80°C for 2 hours, and then coated on a glass sheet and dried at room temperature to form a film.

[0050] Performance test: The ultraviolet absorption performance of the film prepared in Example 3 was tested. Figure 6 As shown: It can be seen that there is strong absorption in the ultraviolet region of 320-510 nanometers.

[0051] Example 4

[0052] A method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film, the preparation method is as follows:

[0053] Mix 5g of polyvinyl pyrrolidone, 87g of anhydrous ethanol, 1.8g of silver sulfate, 2.7g of vitamin C, and 3.5g of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane evenly, react at 60°C for 5 hours, cover it on a glass slide, and dry it at room temperature to form a film.

[0054] Performance test: The ultraviolet absorption performance of the film prepared in Example 4 was tested. Figure 7 As shown: There is strong absorption in the ultraviolet region of 320-580 nanometers.

[0055] Comparative Example 1

[0056] Preparation of pure PVP film: 20g polyvinyl pyrrolidone and 70g anhydrous ethanol were mixed evenly, left at room temperature for 24 hours, covered on a glass sheet, and dried at room temperature to form a film.

[0057] Performance Test:

[0058] The anti-ultraviolet performance of the pure PVP film prepared in Comparative Example 1 was tested by the test method described in Example 1. Figure 8 As shown: It can be seen that there is no absorption in the ultraviolet region. Further testing with an ultraviolet sensor card, such as Fig. 9 As shown, although the comparative example is colorless and transparent after being formed into a film on the glass, after being irradiated with ultraviolet light, it shows color with or without the comparative example, indicating that the comparative example has no anti-ultraviolet function.

[0059] Summarize:

[0060] Comparing Examples 1-4 of the present invention with the comparative example, it can be seen that: the pure PVP film has no anti-ultraviolet properties, while the preparation method of the in-situ grown nanosilver anti-ultraviolet polymer composite film prepared by the present invention can significantly improve the anti-ultraviolet property, and thus can be used as a scrubbable eyeglass film coated on glasses to protect the eyes from ultraviolet damage.

[0061] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various changes or modifications within the scope of the claims, which does not affect the essence of the present invention. In the absence of conflict, the embodiments of the present application and the features in the embodiments can be combined with each other arbitrarily.

Claims

1. An in-situ grown nano silver anti-ultraviolet polymer composite film, characterized in that: Including the following by weight percentage composition:

2. A method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film, characterized in that: The following steps are involved: By weight, 5-20% polyvinyl pyrrolidone, 70-88% ethanol, 0.5-2% silver salt, 0.5-4.5% reducing agent and 1.5-5% silane coupling agent are mixed evenly, reacted at 20-80° C. for 2-24 hours, applied on a glass sheet or eyeglass lens, and dried at room temperature to form a film.

3. The method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film according to claim 2, characterized in that: The ethanol is anhydrous ethanol.

4. The method for preparing an in-situ grown nanosilver anti-ultraviolet polymer composite film according to claim 2, characterized in that: The molecular weight of the polyvinyl pyrrolidone is 8000-500000.

5. The method for preparing an in-situ grown nanosilver anti-ultraviolet polymer composite film according to claim 2, characterized in that: The silver salt is silver nitrate, silver acetate or silver sulfate.

6. The method for preparing an in-situ grown nanosilver anti-ultraviolet polymer composite film according to claim 2, characterized in that: The reducing agent is vitamin C, glucose or tannic acid.

7. The method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film according to claim 2, characterized in that: The silane coupling agent is γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxy(ethyl)silane, γ-methacryloxypropyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy)silane, γ-mercaptopropyl triethoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane or N-β-(aminoethyl)-γ-aminopropyl methyldimethoxysilane.

8. The method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film according to claim 2, characterized in that: The reaction temperature is 50-80° C., and the reaction time is 12-24 hours.

9. The method for preparing an in-situ grown nano-silver anti-ultraviolet polymer composite film according to claim 8, characterized in that: The reaction temperature is 50° C. and the reaction time is 12 hours.

10. An application of the in-situ grown nano silver anti-ultraviolet polymer composite film prepared according to claim 2 in preparing photochromic glasses, characterized in that: The mixed solution after the reaction can be directly applied on the eyeglass lens to form a film.

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