An anti-fog polymer, its preparation method and use
By depositing an inorganic thin film on the polymer surface and forming micro-nano structures using laser scanning, the problems of high cost and unstable performance of existing polymer anti-fogging technologies are solved, achieving low-cost and stable anti-fogging self-cleaning effects, which are suitable for the large-scale production of various polymer materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGDAO UNIV OF TECH
- Filing Date
- 2022-01-21
- Publication Date
- 2026-06-09
AI Technical Summary
Existing polymer anti-fogging technologies are costly, have short-lived and unstable effects, and the anti-fogging effect of traditional sprays is easily affected by temperature, making it difficult to achieve large-scale industrialization.
Anti-fogging self-cleaning polymers are prepared by depositing inorganic thin films on polymer surfaces and forming micro-nano structures using laser scanning. The film thickness and laser parameters are adjusted. Magnetron sputtering or electron beam evaporation deposition methods are used, combined with fiber optic or ultraviolet laser marking machines for scanning.
It achieves low-cost and stable anti-fog effect, with a polymer surface contact angle of ≤5°, has a self-cleaning function, is suitable for a variety of polymer materials, and is suitable for large-scale production.
Smart Images
Figure CN116516300B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of anti-fog polymer preparation technology. By adjusting the polymer surface film layer process, corresponding micro-nano structures are prepared to meet the anti-fog requirements of different polymer materials. Specifically, it relates to an anti-fog polymer, its preparation method and application. Background Technology
[0002] Polymer anti-fogging technology is widely used in the preparation of resin eyeglasses, plastic films for vegetable greenhouses, and flexible transparent substrates. However, when applied to eyeglass manufacturing, this technology is costly, costing nearly 10,000 yuan per square meter, and its anti-fogging effect is short-lived, lasting only about three months. Furthermore, traditional anti-fogging methods use spraying to form organic films, the effectiveness of which decays with temperature and time. For example, anti-fogging treatment using organic-inorganic sprays only lasts 1-2 days, and recycling it results in pollution.
[0003] Therefore, there is an urgent need to develop a technology that is easy to control and can be industrialized on a large scale to improve the anti-fogging and self-cleaning capabilities of polymers. Summary of the Invention
[0004] To address the problems and shortcomings of existing technologies, this invention provides an anti-fogging polymer, its preparation method, and its applications. This invention achieves the goal of preparing an anti-fogging self-cleaning polymer by controlling the micro / nano structure array and its microscopic composition by altering the film thickness of the inorganic thin film and laser scanning parameters.
[0005] To achieve the above-mentioned objectives, the technical solution of the present invention is as follows:
[0006] This invention provides a method for preparing an anti-fog polymer, comprising the following steps:
[0007] (1) Depositing inorganic thin films on polymers;
[0008] (2) Laser scanning is performed on the polymer surface after inorganic film deposition in step (1) to form micro-nano structures on the polymer surface, thereby obtaining an anti-fog self-cleaning polymer.
[0009] Furthermore, the inorganic thin film in step (1) includes an aluminum film, a silicon film, and a silicon-aluminum hybrid film; the deposition thickness of the inorganic thin film is 60nm-1000nm.
[0010] Preferably, the inorganic thin film has a deposition thickness of 200nm-1000nm.
[0011] Furthermore, the deposition method in step (1) includes magnetron sputtering, electron beam evaporation, and thermal evaporation.
[0012] Furthermore, in step (1), the deposition method is to place high-purity silicon particles in a copper crucible or add high-purity aluminum wire to a graphite crucible during electron beam evaporation, and manually adjust the electron beam spot size and the corresponding voltage and current to adjust the evaporation rate. The typical deposition rate is 0.01 Å / s ~ 1000 Å / s until the target thickness is reached.
[0013] In this invention, different equipment has different process parameters, which can be selected according to actual needs.
[0014] Furthermore, the rated power of the laser scanning in step (2) is 1 W-10000 W.
[0015] Preferably, the laser scanning uses a 30W rated power fiber laser.
[0016] Furthermore, the laser source for laser scanning in step (2) is at least one of solid-state laser source, gas phase laser source, infrared laser source, carbon dioxide laser source, ultraviolet laser source, visible light laser source, fiber laser source and near-field scanning optical microscope laser source.
[0017] Furthermore, the wavelength of the laser source is 20 nanometers to 100 micrometers.
[0018] Furthermore, in step (2), the laser scanning speed is 0.01 m / s-10 m / s; the scanning spacing is ≤1 mm; and the filling mode is cross-fill.
[0019] Preferably, the laser scanning speed is 0.3 m / s-3 m / s, the scanning spacing is 0.06 mm, the filling mode is cross-filling, and the scanning power is 1%-100% of the rated power.
[0020] Furthermore, the polymer includes at least one of resin eyeglass lenses, greenhouse plastics, homopolymers, vinyl polymers, block copolymers, carbonized polymers, aromatic polymers, cyclic polymers, polyimide (PI), polyetherimide (PEI), and polyethylene terephthalate (PET).
[0021] Furthermore, the preparation method can be applied to one side of the polymer to form a single-sided micro / nano structure; it can also be applied to both sides of the polymer to form a double-sided micro / nano structure.
[0022] The present invention also provides the application of the anti-fog polymer prepared by the above preparation method in the preparation of eyeglasses, goggles or greenhouses, wherein the anti-fog polymer comprises a base polymer and an inorganic thin film layer, the surface of which has a micro-nano structure and a contact angle ≤5°.
[0023] Furthermore, the anti-fog polymer can be used as the inner surface of the polymer or as the outer surface of the polymer.
[0024] Compared with the prior art, the advantages and beneficial effects of the present invention are:
[0025] 1. This invention uses stable inorganic thin film layers such as silicon, aluminum or mixtures thereof, and laser-processes related materials to generate unique and stable micro-nano structures, forming superhydrophilic contact angles ≤5°, or even 0° under most conditions, overcoming the defects that anti-fogging, stability, uniformity and repeatability cannot be satisfied at the same time.
[0026] 2. In terms of process, the deposition method of the present invention uses magnetron sputtering or electron beam evaporation, etc.; the requirements for laser scanning are low, and fiber laser marking machine or ultraviolet laser marking machine can meet the requirements; the entire preparation method is low in cost and can be completed using industrially stable and mature equipment. Therefore, it can be directly used to improve the properties of various polymers, produce anti-fog self-cleaning polymers, and the parameters can be adjusted according to the compatibility requirements of different polymers, which has the advantage of being scalable. Attached Figure Description
[0027] Figure 1 It is the surface wetting angle of the polymer after treatment in Example 1.
[0028] Figure 2 These are typical laser confocal microscope images of the polymer after treatment in Example 1.
[0029] Figure 3 These are typical laser confocal microscope images of the polymer after treatment in Example 2.
[0030] Figure 4 These are typical laser confocal microscope images of the polymer after treatment in Example 3.
[0031] Figure 5 This is a comparison of the anti-fog effect of the treated resin lens (left) and the untreated lens (right) in Example 1. Detailed Implementation
[0032] The following embodiments better illustrate the content of the present invention. However, the present invention is not limited to the following embodiments.
[0033] Example 1
[0034] A method for preparing an anti-fog resin lens based on a fiber laser marking machine, the specific steps of which are as follows:
[0035] (1) A silicon film was deposited on a resin lens with a thickness of about 8 mm by electron beam evaporation; the thickness of the silicon film was about 250-1000 nm.
[0036] Electron beam silicon deposition process: background vacuum is 10 -4 High-purity silicon (99.9995%) particles were placed in a copper crucible on the Pa scale. The electron beam spot size and brightness were manually adjusted, and the deposition rate was controlled at 1~2 Å / s until the target thickness was reached. The same process was used to deposit a silicon film of the same thickness on the other side of the resin lens.
[0037] (2) Laser scanning of the surface of the resin lens after silicon film deposition in step (1) gathers on the convex surface of the resin lens, forming a micro-nano structure on the resin surface; a fiber laser marking machine with a rated power of 30W is used for laser scanning; the laser scanning conditions are: 90% power; scanning speed 3m / s (or 2.5m / s); filling mode is cross-filling; scanning spacing 0.06 mm; frequency 30kHz; an anti-fog resin lens is obtained. This lens achieves anti-fog on both sides after one laser scan.
[0038] Example 2
[0039] A method for preparing an anti-fog polymer based on an ultraviolet laser marking machine, the specific steps of which are as follows:
[0040] (1) A silicon film was deposited on the convex surface of a resin lens with a thickness of about 8 mm by electron beam evaporation; the thickness of the silicon film was about 200-1000 nm.
[0041] Electron beam silicon deposition process: background vacuum is 10 -4 In the Pa range, high-purity silicon (99.9995%) particles are placed in a copper crucible. The size and brightness of the electron beam spot are manually adjusted, and the deposition rate is controlled at 1~2 Å / s until the target thickness is reached and deposition is stopped.
[0042] (2) Laser scanning of the surface of the resin lens after silicon film deposition in step (1) to form micro-nano structures on the resin surface; a UV laser marking machine with a rated power of 5W is used for laser scanning; the laser scanning conditions are: frequency 30Khz, bandwidth 10ns, 15ns, 18ns respectively; scanning speed 2m / s, 1m / s; scanning spacing 0.06 mm; filling mode is cross filling; other default parameters can be set, and anti-fog polymers are obtained, with most contact angles being 0°.
[0043] Example 3
[0044] A method for preparing an anti-fog resin lens based on a fiber laser marking machine, the specific steps of which are as follows:
[0045] (1) A silicon film was deposited on the convex surface of a resin lens with a thickness of about 8 mm by electron beam evaporation; the thickness of the silicon film was about 200-1000 nm.
[0046] Electron beam silicon deposition process: background vacuum is 10-4 In the Pa range, high-purity silicon (99.9995%) particles are placed in a copper crucible. The size and brightness of the electron beam spot are manually adjusted, and the deposition rate is controlled at 1~2 Å / s until the target thickness is reached and deposition is stopped.
[0047] (2) Laser scanning of the surface of the resin lens after silicon film deposition in step (1) gathers on the convex surface of the resin lens and forms a micro-nano structure on the resin surface; a fiber laser marking machine with a rated power of 30W is used for laser scanning; the laser scanning conditions are: 40% power; scanning speed 2m / s or 1.5m / s; filling mode is cross-filling; scanning spacing 0.06 mm; frequency 30khz; to obtain an anti-fog resin lens.
[0048] The surface wetting angle of the anti-fog resin lens prepared in Example 1 was tested, and the results are as follows: Figure 1 As shown (the straight lines in the figure represent interfaces), the surface contact angle of the anti-fog resin lens is mostly 0°, therefore the polymer is superhydrophilic, thus possessing anti-fog and self-cleaning functions. Furthermore, the deposited film is an inorganic, stable film, so its durability is superior to that of the resin lens itself.
[0049] The surface structure of the anti-fog polymers prepared in Examples 1-3 was observed and photographed using a laser confocal microscope, and the results are as follows. Figure 2-4 As shown, the polymer surface is composed of hierarchical honeycomb micro-nano structures with an outer period of about 70 μm and nested secondary structures. The entire structure contains nanostructures; the amplitude in the depth direction reaches about 50 nm or less. Figure 5 The image shows a comparison of anti-fog resin lenses and untreated resin lenses under foggy conditions. It can be seen that the anti-fog treated resin lenses have excellent anti-fog capabilities.
[0050] Especially in actual production, the size of the resin eyeglass lens after polishing is only a small area of about 35mm in diameter in the center. The anti-fog preparation technology of this invention is highly effective when applied to this small central area. Therefore, the resin lens obtained using the above-described preparation method of this invention is an anti-fog resin lens and can be used to produce resin eyeglasses.
[0051] As illustrated by the above embodiments, the deposition rate can be adjusted by changing the power, electron beam size, and intensity in the thin film deposition process, as long as the target deposition thickness of the thin film is achieved. Furthermore, the polymer properties can be altered by adjusting parameters such as power and scanning speed in the laser scanning process, enabling it to achieve anti-fogging and self-cleaning properties on different polymer surfaces, thus offering the advantage of scalable production.
[0052] In addition, the treated anti-fog polymer surface can be used as the inner surface of the polymer, or as the outer surface, or it can be applied to both sides of the polymer at the same time, such as on the inner surface of protective goggles, while resin glasses require both surfaces to be anti-fog.
[0053] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions claimed by the present invention.
Claims
1. A method for preparing an anti-fogging polymer, characterized in that, Includes the following steps: (1) Depositing an inorganic thin film on a polymer; the inorganic thin film includes an aluminum film, a silicon film, or a silicon-aluminum hybrid film; the deposition thickness of the inorganic thin film is 250 nm-1000 nm; (2) The surface of the polymer after the inorganic thin film deposition in step (1) is scanned by laser to form a micro-nano structure on the polymer surface, thereby obtaining an anti-fog polymer; the laser scanning speed is 2 m / s or 1.5 m / s, the scanning interval is 0.06 mm, and the filling mode is cross-filling; the laser source for the laser scanning is at least one of infrared laser source, ultraviolet laser source and visible light laser source. The preparation method can be applied to one side of the polymer to form a single-sided micro / nano structure; it can also be applied to both sides of the polymer to form a double-sided micro / nano structure.
2. The method for preparing the anti-fog polymer according to claim 1, characterized in that, The deposition methods in step (1) include magnetron sputtering, electron beam evaporation, and thermal evaporation.
3. The method for preparing the anti-fog polymer according to claim 1, characterized in that, The rated power of the laser scanning in step (2) is 1 W-10000 W.
4. The method for preparing the anti-fog polymer according to claim 1, characterized in that, The wavelength of the laser source is 20 nanometers to 100 micrometers.
5. The method for preparing the anti-fog polymer according to claim 1, characterized in that, The polymer includes at least one of polyimide, polyetherimide, and polyethylene terephthalate.
6. The use of the anti-fog polymer prepared by the preparation method according to any one of claims 1-5 in the preparation of resin glasses or eye masks, characterized in that, The anti-fog polymer comprises a base polymer and an inorganic thin film layer, the surface of which has a micro-nano structure and a contact angle ≤5°.