Anti-reflection wear-resistant nano hydrophilic anti-fog lens and preparation method thereof

Abstract

The invention discloses an anti-reflection wear-resistant nano hydrophilic anti-fog lens and a preparation method thereof, and the method comprises the steps: carrying out the injection molding, ultrasonic deep cleaning and surface cleaning treatment of the lens, and obtaining a clean substrate layer; preparing an organic silicon resin hardening liquid, coating the surface of the substrate layer with the organic silicon resin hardening liquid, and curing to obtain an organic silicon resin layer; preparing a nano hydrophilic coating; cleaning the surface of the organic silicon resin layer, keeping the surface dry, and activating by using plasma equipment; and coating the surface of the activated organic silicon resin layer with a nano hydrophilic coating, and then baking at the temperature of 40-120 DEG C for 6-0.5 h to obtain the nano hydrophilic coating. According to the invention, a nano hydrophilic coating containing modified silicon dioxide is adopted to be in covalent bond connection with an active group in the organic silicon resin layer, so that lasting hydrophilic modification of the substrate layer is realized, a water drop contact angle is less than 6 degrees, super-hydrophilicity can be presented without illumination, and the super-hydrophilic group has low chemical activity, is not easy to pollute and is convenient to clean; the service life is long.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-fog hydrophilic lenses, and in particular to an anti-reflection, wear-resistant, nano-hydrophilic anti-fog lens and a preparation method thereof, as well as a swimming goggle. Background Art

[0002] In recent years, nano-superhydrophilic technology has gradually become a research hotspot. This technology utilizes the special surface properties of nano-materials to endow the material surface with superhydrophilicity, thereby achieving multiple effects such as anti-fogging and easy cleaning. In the field of swimming goggles, the application of nano-superhydrophilic technology can significantly improve the anti-fog performance of swimming goggles, providing swimmers with a clearer and more comfortable vision and higher safety. However, due to the instability of the nano-hydrophilic coating on swimming goggles, poor wear resistance, and immature preparation formulations / processes, such swimming goggles still face problems of poor durability and short service life.

[0003] In view of this, it is necessary to provide an anti-reflection, wear-resistant, nano-hydrophilic anti-fog lens and a preparation method thereof to overcome the above defects. Summary of the Invention

[0004] The purpose of the present invention is to provide an anti-reflection, wear-resistant, nano-hydrophilic anti-fog lens and a preparation method thereof, aiming to improve the problems of poor durability of the nano-hydrophilic coating on existing swimming goggles and short service life, and to extend the service life of the lens.

[0005] To achieve the above purpose, the present invention provides a preparation method for an anti-reflection, wear-resistant, nano-hydrophilic anti-fog lens, including:

[0006] Step S10: Inject, ultrasonically clean deeply, and perform surface cleaning treatment on the lens material to obtain a clean substrate layer;

[0007] Step S20: Prepare an organosilicon resin hardening solution, and coat the organosilicon resin hardening solution on the surface of the substrate layer, and obtain an organosilicon resin layer after curing;

[0008] Step S30: Prepare a nano-hydrophilic coating by taking 98.65 - 99.30 wt% of ultrapure water, 0.70 - 1.05 wt% of modified silica, and less than 0.30 wt% of a surfactant;

[0009] Step S40: Clean the surface of the organosilicon resin layer, then keep the surface dry, and activate it using a plasma device;

[0010] Step S50: Coat the nano-hydrophilic coating on the surface of the activated organosilicon resin layer, and then bake it in an environment of 40°C - 120°C for 6 h - 0.5 h, thereby preparing a nano-hydrophilic coating on the side of the organosilicon resin layer away from the substrate layer.

[0011] In a preferred embodiment, in step S20, the silicone resin hardening solution comprises raw materials in the following mass percentages:

[0012] 23% - 27% of silica, 0.5% - 1.5% of 1-methoxy-2-propanol, 32% - 36% of ethanol, 21% - 25% of isopropanol, 7% - 9% of ethylene glycol monoethyl ether acetate, 1.5% - 2.5% of acetic acid, and the balance being water.

[0013] In a preferred embodiment, in step S20, the coating process of the silicone resin hardening solution specifically comprises:

[0014] Immerse the substrate layer in the silicone resin hardening solution for 3 s - 9 s, or coat the silicone resin hardening solution on one or both sides of the substrate layer through a slow-drawing device, and then set the curing temperature at 60°C - 120°C and cure for 360 min - 120 min, thereby obtaining a silicone resin layer on one or both sides of the substrate layer.

[0015] In a preferred embodiment, the raw materials of the modified silica comprise 0.1% - 0.2 wt% of silica and 0.7 wt% of 1-butylamino-N,N-dimethyl-N-(3-sulfopropyl)-betaine; the surfactant comprises less than 0.1 wt% of fatty alcohol polyoxyethylene ether.

[0016] In a preferred embodiment, the average particle size of the modified silica is 10 nm - 100 nm.

[0017] In a preferred embodiment, in step S40, the activation using a plasma device specifically comprises:

[0018] The plasma device uses a radio frequency power supply with a power of 260 W - 280 W. The vacuum degree of the device during activation is 16 pA - 28 pA. The ratio of oxygen and argon passed through is 3:1. The gas mixing time is 30 s - 40 s, and the treatment time is 250 s - 350 s.

[0019] In a preferred embodiment, the thickness of each silicone resin layer is 7 μm - 15 μm.

[0020] In a preferred embodiment, after step S20, it further comprises: electroplating on one side of one of the silicone resin layers away from the substrate layer to obtain an electroplated color layer.

[0021] The present invention also provides an antireflective, wear-resistant, and nano-hydrophilic and antifogging lens, which is prepared by using the preparation method of the antireflective, wear-resistant, and nano-hydrophilic and antifogging lens according to any one of the above embodiments.

[0022] The present invention also provides a pair of goggles, which includes the antireflective, wear-resistant and nano-hydrophilic antifogging lens as described in the above-mentioned embodiment.

[0023] For the antireflective, wear-resistant and nano-hydrophilic antifogging lens and its preparation method provided by the present invention, first, an organosilicon resin hardening solution is used to improve the wear resistance of the substrate layer and achieve an antireflective effect. Secondly, a nano-hydrophilic coating containing modified silica is used. It has both stable hydrophilic groups and reactive groups, and can form covalent bonds with the reactive groups in the organosilicon resin layer to achieve permanent hydrophilic modification of the substrate layer. The water contact angle on the surface of the modified nano-hydrophilic coating is less than 6°. It shows superhydrophilicity without light irradiation. The superhydrophilic group has low chemical activity, is not easily contaminated, is convenient to clean, and has a long service life. In addition, the solvent of the nano-hydrophilic coating used on the lens is water, which does not contain various film-forming aids such as ethers, has no odor or has a smell but is not irritating, improving the use safety. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0025] Figure 1 It is a flowchart of the preparation method of the antireflective, wear-resistant and nano-hydrophilic antifogging lens provided by the present invention;

[0026] Figure 2 It is a coated TEM image (thickness detection image) of the nano-hydrophilic coating of the lens sample

[0027] Figure 3 It is the water film forming image of the antifogging water immersion test of the lens sample at the 600th hour;

[0028] Figure 4 It is the result image of the cross-cut test of the lens sample;

[0029] Figure 5 It is the result image of the 3M adhesion test of the lens sample;

[0030] Figure 6 It is a transmittance detection table of three groups of lens samples;

[0031] Figure 7 It is a diagram of the transmittance spectral curve of the lens sample;

[0032] Figure 8 It is a water droplet angle detection image of a sample of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] In order to make the objectives, technical solutions, and beneficial technical effects of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described in this specification are only for explaining the present invention and not for limiting the present invention.

[0034] It should also be understood that the terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. As used in this specification of the present invention and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an", and "the" are intended to include the plural forms.

[0035] It should be further understood that the term "and / or" used in this specification of the present invention and the appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.

[0036] In an embodiment of the present invention, a method for preparing an anti-reflection, wear-resistant, and nano-hydrophilic anti-fog lens is provided, which is used to prepare wear-resistant and anti-reflection, long-lasting super-hydrophilic anti-fog lenses and goggles, and achieve a long-lasting hydrophilic anti-fog effect.

[0037] As Figure 1 shown, the method for preparing an anti-reflection, wear-resistant, and nano-hydrophilic anti-fog lens includes steps S10 - S50.

[0038] Step S10: Inject, ultrasonically clean deeply, and perform surface cleaning treatment on the lens material to obtain a clean substrate layer. Among them, the lens material can be made of transparent materials such as PC (Polycarbonate), PMMA (PolymethylMethacrylate), etc.

[0039] Step S20: Prepare an organosilicon resin hardening solution, and coat the surface of the substrate layer with the organosilicon resin hardening solution, and obtain an organosilicon resin layer after curing.

[0040] Specifically, the organosilicon resin hardening solution includes the following raw materials by mass percentage: 23% - 27% of silicon dioxide, 0.5% - 1.5% of 1-methoxy-2-propanol, 32% - 36% of ethanol, 21% - 25% of isopropanol, 7% - 9% of ethylene glycol monoethyl ether acetate, 1.5% - 2.5% of acetic acid, and the rest is water. In a preferred embodiment, the raw materials of the organosilicon resin hardening solution include: 25% of silicon dioxide, 1.0% of 1-methoxy-2-propanol, 34% of ethanol, 23% of isopropanol, 8% of ethylene glycol monoethyl ether acetate, 2% of acetic acid, and 7% of water.

[0041] The coating process of the silicone resin curing liquid specifically includes:

[0042] Soak the substrate layer in the silicone resin hardening liquid for 3s-9s, so that both sides of the substrate layer are coated with the hardening liquid to achieve double-sided hardening; or apply the silicone resin hardening liquid to one or both sides of the substrate layer through a slow-pull device to achieve single-sided hardening. Then set the curing temperature to 60℃-120℃ and cure for 360min-120min to obtain a silicone resin layer on one or both sides of the substrate layer. It should be noted that the higher the curing temperature, the less time required, that is, the curing time corresponding to a curing temperature of 60℃ is 360min, and the curing time corresponding to a curing temperature of 120℃ is 120min.

[0043] Furthermore, the thickness of each silicone resin layer is 7 μm-15 μm. The silicone resin layer mainly improves the wear resistance and anti-reflection effect of the lens. In the swimming goggles prepared by the lens, the wear resistance test of chlorine water is carried out using a wear test machine and a 4.5*4.5 microfiber dust-free cloth as auxiliary material.

[0044] Test method: Fold the microfiber dust-free cloth in half twice, dip it into the prepared 500ppm chlorine aqueous solution, wet the surface of the dust-free cloth without water droplets, and fix the wetted dust-free cloth on the friction head. Apply a 500g load → timed 500ppm chlorine aqueous solution to keep it moist for 500 round trips (40 round trips / min), stroke: 15mm°. Confirm the effect every 1000 times, and stop the test immediately if the anti-fog disappears. There should be no visible scratches, wear and tear, and the water drop angle is less than 20°±1 (water film formation) within the friction range of the lens.

[0045] The test results show that the water drop angle is 3.28° when tested 1000 times; 4.37° when tested 2000 times; 4.96° when tested 3000 times; 5.7° when tested 4000 times, and no water film is formed. It can be seen from the results that the organic silicone resin layer prepared by the present invention makes the lens have excellent friction resistance and can resist friction in daily use by consumers. The daily service life is expected to reach about 3 years.

[0046] Step S30: 98.65-99.30wt% ultrapure water, 0.70-1.05wt% modified silicon dioxide and less than 0.30wt% surfactant are used to prepare a nano hydrophilic coating. The "ultrapure water" here refers to ultrapure water that has been filtered multiple times, that is, the water has the highest quality purity. Of course, ultrapure water can be regarded as deionized water that has reached a predetermined cleanliness level.

[0047] Further, the raw materials of the modified silica include 0.1%-0.2 wt% of silica and 0.7 wt% of 1-butylamino-N,N-dimethyl-N-(3-sulfopropyl)-inner salt; the surfactant includes less than 0.1 wt% of fatty alcohol polyoxyethylene ether. Among them, the average particle size of the modified silica is 10 nm - 100 nm. It should be noted that in the prior art, the hydrophilic function is mainly achieved by the hydrophilicity of polyvinyl alcohol and the hydrophilicity and adhesion of modified silica sol. Different from this, the nano-hydrophilic coating of the present invention realizes the hydrophilic function by an inorganic-organic composite method, and the silica is effectively adhered after being modified by the above special hydrophilic groups.

[0048] Step S40: Clean the surface of the silicone resin layer and then keep the surface dry, and then activate it with a plasma device, so as to form a large number of Si-OH groups on the surface of the silicone resin layer.

[0049] Specifically, the activation using the plasma device specifically includes: the plasma device uses a radio frequency power supply with a power of 260 W - 280 W (preferably 270 W), the vacuum degree of the device during activation is 16 pA - 28 pA (preferably 18 pA), the ratio of oxygen and argon passed through is 3:1, the gas mixing time is 30 s - 40 s, and the treatment time is 250 s - 350 s.

[0050] Step S50: Coat the nano-hydrophilic coating on the activated surface of the silicone resin layer. The modified silica groups in the hydrophilic material are chemically bonded to the activated surface SI-OH groups of the silicone resin layer, and then bake at 40°C - 120°C for 6 h - 0.5 h for an accelerated reaction combination, so as to obtain a nano-hydrophilic coating on the side of the silicone resin layer away from the substrate layer. The higher the baking temperature, the less time is required, that is, 6 h of baking is required at 40°C, and 0.5 h of baking is required at 120°C. Among them, after testing (coating the nano-hydrophilic coating on the surface of a glass slide), combined Figure 2 with the shown coated TEM (Transmission Electron Microscope) image, the thickness of the nano-hydrophilic coating is 20 nm - 100 nm, which is significantly reduced compared with the nano-hydrophilic coating film of the traditional lens (the thickness is 250 nm - 500 nm).

[0051] Among them, the nano-hydrophilic coating has the following properties:

[0052] 1) Superhydrophilicity: The water droplet contact angle is less than 6°, showing superhydrophilicity;

[0053] 2) No need for light: Superhydrophilicity can be achieved without light;

[0054] 3) Persistence: The super-hydrophilic groups are of low chemical activity and are not easily contaminated, enabling persistent super-hydrophilicity.

[0055] 4) Rub resistance and water resistance: The super-hydrophilic coating maintains its hydrophilicity after being wiped and soaked in water.

[0056] 5) Anti-fouling property: When rinsed with water, the oily marker stains on the surface float up and flow down under the action of water, achieving the anti-fouling function.

[0057] 6) Anti-static property: It prevents the accumulation of static electricity on the surface, thereby preventing the adsorption of charged dust.

[0058] Further, in some embodiments, after step S20, it further includes: electroplating on the side of one of the silicone resin layers away from the substrate layer to obtain an electroplated color layer. That is, the electroplated color layer is located between the silicone resin layer and the nano-hydrophilic coating, thus having an anti-ultraviolet effect.

[0059] One: Take the above-mentioned lens products for anti-fogging performance testing (tap water immersion method):

[0060] Test conditions: The equipment is a beaker container and tap water, and the auxiliary material is tap water at room temperature;

[0061] Test method: Put the product into the container and then add an appropriate amount of tap water (at room temperature) to submerge the product; Check the anti-fogging performance at 48 / 144 / 240 / 360 / 600h, record the results, and test until the anti-fogging fails, and record the total failure time;

[0062] Judgment criteria: Check the anti-fogging performance by placing it 5 cm above the 80° water surface for 3 s before and after the test; After the lens is static for 6 s, there is no steam or water droplets on the anti-fogging surface. After the lens is static for 20 s, there is no fogging or dew condensation on the anti-fogging surface of the lens, and the coating does not peel off; The standard is 600h, a water film is formed, and the water contact angle < 20°.

[0063] Test results: As shown in Figure 3 The water contact angle diagram at the 600th hour shows that all the above tests are passed.

[0064] Test conclusion: Assuming the average usage frequency is 2 hours each on Saturdays and Sundays, there are 104 Saturdays in a year, 104 * 2h * 3 years = 624h; If consumers maintain and use it normally, the experimental data shows that it can support about 3 years.

[0065] Two: Take the above-mentioned lens products for anti-fog film layer adhesion and cross-cut test:

[0066] Test conditions: The equipment is a cross-cut knife, and the auxiliary material is commercially available 3M600 tape;

[0067] Test method: Use a blade and a flexible ruler to gently cut 11 lines horizontally and vertically on the lens (both sides), with a 1 mm interval between each line (make sure the ruler does not touch the already cut lines). There are a total of 100 squares. The blade should cut through the coating but not penetrate into the lens substrate under the coating to prevent surface bulging. Use 3M invisible tape (here it is Magic Tape, No. 810, 19 mm wide), stick it on the 100 squares, and tear the tape backward (180°) at a slightly faster and steady speed (do not use brute force). For the invisible tape with a long test interval, the outermost two circles are torn off and not used each time, and the invisible tape cannot be reused.

[0068] Judgment criteria: First, check whether the tape after being pulled off adheres to the coating. Then, use reflected light to check the squares on the lens (or view with a magnifying glass). If the hard film peels off, there will be white light instead of colored light reflected. If the multi-layer film delaminates, the color will change. Delamination at the edge of the square line is not considered defective, but if an entire square delaminates, it is judged as defective.

[0069] Test results: As Figure 4 shown, it is the hundred-grid test result diagram, and there is no peeling in the hundred-grid test; as Figure 5 shown, it is the 3M adhesion test result diagram, and there is no peeling in the 3M test.

[0070] Test conclusion: The adhesion ISO grade is 0 (ISO grade 0 = ASTM grade 5B), the adhesion is very firm and has a long service life, and the experimental data supports no peeling for 3 years.

[0071] Third, randomly select three samples of the substrate layer and three samples of the above-mentioned lens finished products, and then conduct spectral detection on the lens samples. As Figure 6 shown, it is the transmittance detection form of the three samples. It can be seen that the present invention indeed has a significant improvement in anti-reflection. Among them, "material" is the substrate layer, and "hardening and anti-fogging" is the combination of the silicone resin layer and the nano-hydrophilic coating of the present invention. As Figure 7 shown, it is the spectral diagram of the lens sample. It can be intuitively seen that the "hardening and anti-fogging" film layer of the present invention has a higher transmittance. As Figure 8 shown, it is the water contact angle detection diagram of one of the samples of the present invention. The left water contact angle is 5.371°, and the right is 5.370°, indicating good hydrophilic and anti-fogging functions.

[0072] The present invention also provides an anti-reflection, wear-resistant and nano-hydrophilic anti-fog lens, which is prepared by using the preparation method of the anti-reflection, wear-resistant and nano-hydrophilic anti-fog lens described in any one of the above embodiments.

[0073] The present invention also provides a swimming goggle, including the anti-reflection, wear-resistant and nano-hydrophilic anti-fog lens described in the above embodiment.

[0074] In summary, the antireflective, wear-resistant, and nano-hydrophilic and antifog lens provided by the present invention first uses an organosilicon resin hardening solution to improve the wear resistance of the substrate layer and achieve an antireflective effect. Secondly, a nano-hydrophilic coating containing modified silica is used, which has both stable hydrophilic groups and reactive groups, and can form covalent bonds with the reactive groups in the organosilicon resin layer to achieve permanent hydrophilic modification of the substrate layer. The water contact angle on the surface of the modified nano-hydrophilic coating is less than 6°, and it exhibits superhydrophilicity without light irradiation. This superhydrophilic group has low chemical activity, is not easily contaminated, is convenient to clean, and has a long service life. In addition, the solvent of the nano-hydrophilic coating used on the lens is water, which does not contain various film-forming aids such as ethers, has no odor or has a non-irritating smell, and improves the use safety.

[0075] The present invention is not limited only to what is described in the specification and embodiments. Therefore, additional advantages and modifications can be easily achieved by those skilled in the art. Thus, without departing from the spirit and scope of the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details, representative devices, and illustrated examples shown and described herein.

Claims

1. A preparation method of an antireflection, wear-resistant, nano-hydrophilic and antifogging lens, characterized in that, Including: Step S10: Inject, ultrasonically and deeply clean, and surface clean the lens material to obtain a clean substrate layer; Step S20: Prepare an organosilicon resin hardening solution, coat the surface of the substrate layer with the organosilicon resin hardening solution, and obtain an organosilicon resin layer after curing; Step S30: Prepare a nano-hydrophilic coating by taking 98.65 - 99.30 wt% of ultrapure water, 0.70 - 1.05 wt% of modified silica, and less than 0.30 wt% of a surfactant; Step S40: Clean the surface of the organosilicon resin layer and then keep the surface dry, and then activate it using a plasma device; Step S50: Coat the nano-hydrophilic coating on the surface of the activated organosilicon resin layer, and then bake it in an environment of 40°C - 120°C for 6 h - 0.5 h, thereby preparing a nano-hydrophilic coating on the side of the organosilicon resin layer away from the substrate layer.

2. The preparation method of the antireflection, wear-resistant, nano-hydrophilic and antifogging lens according to claim 1, characterized in that, In step S20, the organosilicon resin hardening solution includes raw materials in the following mass percentages: 23% - 27% of silica, 0.5% - 1.5% of 1-methoxy-2-propanol, 32% - 36% of ethanol, 21% - 25% of isopropanol, 7% - 9% of ethylene glycol monoethyl ether acetate, 1.5% - 2.5% of acetic acid, and the balance is water.

3. The preparation method of the antireflection, wear-resistant, nano-hydrophilic and antifogging lens according to claim 2, characterized in that, In step S20, the coating process of the organosilicon resin hardening solution specifically includes: Immerse the substrate layer in the organosilicon resin hardening solution for 3 s - 9 s, or coat the organosilicon resin hardening solution on one or both sides of the substrate layer through a slow-drawing device, and then set the curing temperature at 60°C - 120°C and cure for 360 min - 120 min, thereby preparing an organosilicon resin layer on one or both sides of the substrate layer.

4. The preparation method of the antireflection, wear-resistant, nano-hydrophilic and antifogging lens according to claim 1, characterized in that, The raw materials of the modified silica include 0.1% - 0.2 wt% of silica and 0.7 wt% of 1-butylamino-N,N-dimethyl-N-(3-sulfopropyl)-betaine; the surfactant includes less than 0.1 wt% of fatty alcohol polyoxyethylene ether.

5. The preparation method of the anti-reflection, wear-resistant, nano-hydrophilic and anti-fog lens according to claim 4, characterized in that, The average particle size of the modified silica is 10 nm - 100 nm.

6. The preparation method of the antireflection, wear-resistant, nano-hydrophilic and antifogging lens according to claim 4, characterized in that, In step S40, the activation using a plasma device specifically includes: The plasma device uses a radio frequency power supply with a power of 260 W - 280 W. During activation, the vacuum degree of the device is 16 pA - 28 pA, the ratio of oxygen and argon passed through is 3:1, the gas mixing time is 30 s - 40 s, and the treatment time is 250 s - 350 s.

7. The preparation method of the antireflection, wear-resistant, nano-hydrophilic and antifogging lens according to claim 1, characterized in that, The thickness of each organosilicon resin layer is 7 μm - 15 μm.

8. The preparation method of the antireflection, wear-resistant, nano-hydrophilic and antifogging lens according to claim 1, characterized in that, After step S20, it further includes: electroplating on the side of one of the organosilicon resin layers away from the substrate layer to prepare an electroplated color layer.

9. An anti-reflection, wear-resistant and nano-hydrophilic anti-fog lens, characterized in that, Prepared by using the preparation method of an antireflection, wear-resistant, and nano-hydrophilic and antifogging lens according to any one of claims 1 - 8.

10. A pair of swimming goggles, characterized in that, Including an antireflection, wear-resistant, and nano-hydrophilic and antifogging lens according to claim 9.

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