A waterproof and fog-proof and radiation-proof lens and its preparation method

Abstract

The present invention discloses a waterproof and anti-radiation lens and a preparation method thereof, relating to the technical field of lenses. In the present invention, a nano-sheet carbon film is deposited, and carbon nanotubes are vertically grown and connected in series to form a conductive network, thereby forming a conductive loss of electromagnetic radiation. Then, a magnetic layer and a non-magnetic layer are sequentially deposited to form an anti-radiation layer. While preventing water fog, a magnetic absorption network can be formed to promote magnetic loss and improve the anti-radiation ability of the lens. Moreover, the existence of multiple interfaces accelerates the conversion of electromagnetic waves into heat energy, improving the anti-radiation and waterproof fog properties of the lens. Then, the anti-radiation layer is modified with hexamethylenediamine methyltrimethoxysilane, 2-amino-3-chloro-6-bromobenzoic acid, cinnamitrile, dimethylaminopropylamine, and (3S)-3-amino-N-cyclohexyl-2-oxohexanamide to effectively absorb blue light and achieve the effect of filtering blue light. The waterproof and anti-radiation lens prepared by the present invention has the effects of preventing water fog, anti-radiation, and filtering blue light.

Description

Technical Field

[0001] The present invention relates to the technical field of lenses, and particularly to a waterproof and anti-radiation lens and a preparation method thereof. Background Art

[0002] Blue light refers to light with a wavelength in the range of 380 - 500 nm. Blue light is a type of visible light. It has a short wavelength and high energy and can directly penetrate the lens and reach the retina at the bottom of the eye. Among them, the short-wave blue light with a wavelength between 385 - 445 nm has the greatest harm to the retina. Moreover, there are many types of anti-blue light resin lenses on the market. The anti-blue light effects of resin lenses with different refractive indices are different, but the overall anti-blue light effect is relatively low, and they are just taking advantage of the market hot spot to win sales. In addition, with the gradual expansion of the resin glasses market, its resin lenses have also received more and more attention from consumers. Therefore, with the diversification of consumer requirements, all aspects of the performance and technology of resin lenses are constantly being improved and perfected.

[0003] Currently, mainly on the basis of hardened resin lenses, an anti-reflection film layer, a top waterproof layer, etc. are deposited through a vacuum coating method to achieve the effects of enhancing the transmittance and protecting the lens. The current optical lenses have poor anti-radiation performance. During long-term use by wearers, there is a risk of radiation damaging the eyes. At the same time, most current lenses are prone to water mist condensation. Although it is not harmful itself, it seriously affects daily life. The market often uses the method of hydrophilic coating to solve this problem, but the existing hydrophilic coatings cannot adhere tightly to the surface, leaving gaps between the coatings and the lenses, and the generated water droplets are easy to enter the glasses. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterproof and anti-radiation lens and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A waterproof and anti-radiation lens is prepared by the following method. The resin glass is hardened to obtain pretreated resin glass; then an anti-radiation layer glass is formed through the first deposition treatment, the second deposition treatment, the third deposition treatment, and sputtering deposition treatment, and then modified treatment is carried out.

[0006] Further, the resin glass is one of allyl diglycol carbonate glass, acrylic glass, polyurethane glass, or polycarbonate glass.

[0007] Further, the first deposition treatment is to place the pretreated resin glass in a mixed atmosphere of methane and hydrogen, and prepare the nano-sheet carbon film glass by microwave plasma; the second deposition treatment is to place the nano-sheet carbon film glass in a mixed atmosphere of nickel nitrate, nitrogen and hydrogen, and after reacting for a predetermined time, introduce methane and prepare the composite carbon film glass by microwave plasma; the third deposition treatment is to place the composite carbon film glass in an electroplating solution, and perform double-pulse electroplating under magnetic stirring to obtain the magnetic layer glass; the sputtering deposition treatment uses titanium dioxide as the target and is performed by pulsed laser deposition.

[0008] Further, the modification treatment includes the following steps: mixing the radiation-proof layer glass with hexamethylenediamine methyltrimethoxysilane solution, and stirring and reacting to obtain the preliminarily modified glass; then mixing the preliminarily modified glass with 2-amino-3-chloro-6-bromobenzoic acid, heating and reacting to a predetermined time, cooling, fishing out, then immersing in ice water, standing, filtering, washing and drying to obtain the lens precursor; then mixing the lens precursor, cinnamonitrile and dimethylaminopropylamine, stirring and heating and reacting for a period of time, cooling, filtering and washing to obtain the isatinone compound glass; then mixing the isatinone compound glass with (3S)-3-amino-N-cyclohexyl-2-oxohexanamide, reacting at room temperature for a period of time, distilling, then adding isopropanol, stirring, filtering, washing and drying.

[0009] Further, a preparation method of a waterproof and anti-radiation lens includes the following preparation steps:

[0010] (1) Place the pretreated resin glass in a container, introduce hydrogen until the air pressure is 3×10 3 ~5×10 3 Pa, pretreat for 7 - 13 min at 300 - 400 W, then introduce methane and hydrogen until the air pressure is 6×10 3 ~9×10 3 Pa, deposit for 50 - 66 min at 400 - 500 W to obtain the nano-sheet carbon film glass;

[0011] (2) Place the nano-sheet carbon film glass in a container, evacuate to 1×10 -3 ~5×10 -3 Pa, heat to 210 - 290 °C, introduce nickel nitrate, hydrogen and nitrogen, after introducing for 30 - 42 min, raise the temperature to 500 - 550 °C, introduce methane at 80 - 120 cm 3 / min until the air pressure is 28 - 34 Pa, react for 29 - 41 min at 200 - 300 W, then under nitrogen atmosphere, cool down to room temperature to obtain the composite carbon film glass;

[0012] (3) Place the composite carbon film glass in an electroplating solution that is 4 to 10 times the mass of the composite carbon film glass, heat it to 50 to 64 °C, stir at 200 to 300 rpm, and apply double-pulse electroplating for 22 to 40 min under a magnetic field of 10 to 16 T to obtain magnetic layer glass;

[0013] (4) Use titanium dioxide as the target, place the magnetic layer glass at a distance of 40 to 50 mm, and deposit for 19 to 31 min in an argon atmosphere with a laser energy density of about 1.5 to 2.0 J / cm 2 ², a repetition frequency of 5 Hz, and a pulse width of 20 to 25 ns to obtain radiation-proof layer glass;

[0014] (5) Mix the radiation-proof layer glass, hexamethylenediaminomethyltrimethoxysilane, absolute ethanol, and deionized water in a mass ratio of 1:0.5:8:2.5 to 1:1.5:21:7.5, react at 100 to 200 rpm for 50 to 68 min, then fish out and wash with deionized water 4 to 8 times to obtain preliminarily modified glass; Mix N,N-dimethylformamide, preliminarily modified glass, 2-amino-3-chloro-6-bromobenzoic acid, and potassium carbonate in a mass ratio of 38:1:0.8:0.5 to 52:1:2.1:0.5, heat to 50 to 66 °C, react for 6 to 12 h, then cool to room temperature, fish out, immerse in ice water that is 5 to 12 times the mass of the preliminarily modified glass, let stand for 28 to 42 min, then filter, wash with deionized water 3 to 5 times, and dry at 50 to 62 °C for 4 to 8 h to obtain the lens precursor;

[0015] (6) Under nitrogen protection, mix the lens precursor, cinnamonitrile, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate, cesium carbonate, and acetonitrile in a mass ratio of

[0016] 1:0.8:0.8:0.03:3:5:19 to 1:1.6:1.3:0.03:7:10:26, react at 100 to 200 rpm and 110 to 140 °C for 8 to 13 h, then cool to room temperature, filter, wash with ethyl acetate 4 to 6 times, and dry at 40 to 53 °C for 3 to 6 h to obtain isatinone compound glass;

[0017] (7)Disperse the isatinone compound glass in acetonitrile which is 55 - 63 times the mass of the isatinone compound glass. Under a nitrogen atmosphere, cool it to 0 - 5 °C in an ice - water bath, then add tert - butyl hypochlorite which is 1.0 - 1.6 times the mass of the isatinone compound glass and (3S)-3 - amino - N - cyclohexyl - 2 - oxohexanamide which is 0.8 - 1.4 times the mass of the isatinone compound glass. Let it rise to room temperature naturally. After reacting for 18 - 24 h, distill at a vacuum of 0.01 - 0.05 MPa and 79 - 85 °C for 8 - 12 h. Then add isopropanol which is 8 - 13 times the mass of the isatinone compound glass, stir at 100 - 200 rpm for 32 - 48 min, filter, wash with isopropanol 5 - 7 times, and dry at 40 - 60 °C for 4 - 8 h to obtain a waterproof and anti - radiation lens.

[0018] Further, the preparation method of the pretreated resin glass in step (1) is: Immerse the resin glass in an organosilicon hardening solution which is 5 - 10 times the mass of the resin glass, let it stand for 3 - 7 min, and then cure at 80 - 90 °C for 30 - 46 min.

[0019] Further, the hydrogen flow rate in step (1) is 130 - 200 cm 3 / min; methane and hydrogen are introduced according to a flow rate ratio of 1:3 - 1:5.

[0020] Further, nickel nitrate, hydrogen, and nitrogen in step (2) are introduced according to a flow rate ratio of 1:2:2 - 1:4:4, and the hydrogen flow rate is 70 - 100 cm 3 / min.

[0021] Further, the electroplating solution formula in step (3) is: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest is deionized water.

[0022] Further, the double - pulse electroplating parameters in step (3) are: the pulse frequency is 2 kHz, the forward pulse current density is 5 - 9 A / dm 2 , the duty cycle is 0.30 - 0.42, the reverse pulse current density is 0.9 - 1.5 A / dm 2 , and the duty cycle is 0.17 - 0.32.

[0023] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0024] The present invention uses resin glass as the substrate, coats an anti - radiation layer, and then modifies it to obtain a lens, making it have the functions of anti - radiation, anti - blue light, and waterproofing.

[0025] First, the present invention performs a hardening treatment to form a silicon layer on the surface of plexiglass; then a first deposition treatment is carried out. Microwave plasma discharge activates methane, and a chemical reaction occurs on the surface of the silicon layer to form carbon nanosheets, which are intertwined to form a carbon film; then a second deposition treatment is carried out. Nickel nitrate is vaporized and mixed with hydrogen and introduced. Since hydrogen can reduce nickel nitrate, nickel metal particles are formed and deposited on the surface of the carbon film. Then, ammonia gas is generated by the high temperature of a nitrogen-hydrogen mixed gas, effectively etching the nickel metal to form island-like particles. Then, using nickel as a catalyst, carbon nanotubes are grown vertically to the island-like structure through microwave plasma chemical vapor deposition, and are intertwined with each other to form a large number of voids, constituting impedance matching. And the carbon films are connected in series to form a large conductive network, which can convert electromagnetic radiation into current and dissipate it as heat, making the lens radiation-resistant. At the same time, it can prevent water vapor condensation, making the lens have an anti-fog effect; then a third deposition treatment is carried out. Iron-nickel alloy is electroplated using forward and reverse double pulses. By changing the direction, the surface protrusions are dissolved. At the same time, an external magnetic field is applied to make the surface pores disappear and refine the grains, forming a magnetic layer with uniform thickness and flatness. Then, non-magnetic titanium dioxide is sputtered and coated. While improving the anti-fog property of the lens, magnetic coupling is generated between magnetic particles to form a magnetic absorption network, promoting the magnetic loss of electromagnetic radiation and improving the anti-radiation ability of the lens; in addition, the existence of multiple interfaces and the resonance generated by magnetic particles act on electromagnetic waves together, making the lens have a strong electromagnetic radiation attenuation ability, accelerating the conversion of electromagnetic waves into heat energy, and improving the anti-radiation and anti-fog properties of the lens.

[0026] Secondly, titanium dioxide on the surface of the radiation-resistant layer is modified with hexamethylenediaminomethyltrimethoxysilane to introduce amino groups, which react with the chloride ions of 2-amino-3-chloro-6-bromobenzoic acid and are grafted onto the surface of titanium dioxide; then the cyano group of phenylacetonitrile and the amino group of dimethylaminopropylamine react with the bromide ion and carboxyl group of 2-amino-3-chloro-6-bromobenzoic acid respectively, and form a ring under the action of a catalyst to form an isatinone compound, which effectively absorbs blue light, thereby reducing the transmission of blue light and achieving a blue light filtering effect, making the lens have a blue light blocking effect; then (3S)-3-amino-N-cyclohexyl-2-oxohexanamide reacts with 2-amino-3-chloro-6-bromobenzoic acid to undergo an azo reaction to generate an azo group, which acts together with the isatinone compound to improve the blue light blocking property of the lens. Detailed implementation mode

[0027] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.

[0028] The method provided by the present invention is described in detail through the following embodiments. The test methods for various indicators of the waterproof and fog-proof and radiation-proof lens produced in the following embodiments are as follows:

[0029] Waterproof and fog-proof property: Take the examples and comparative examples with equal areas for the water vapor condensation effect test. After placing them above hot water for 30 s and then leaving above the hot water, measure the time for the water mist on the lens to dissipate, and after irradiating with γ-rays, observe the water mist condensation on the surface.

[0030] Radiation protection property: Take the examples and comparative examples with equal thicknesses for the radiation shielding effect test. Refer to EJ / T 793 and use a γ-ray irradiator and 99 a Tc isotope ray source to test the samples.

[0031] Blue light protection property: Take the examples and comparative examples with equal thicknesses for the blue light transmittance effect test. Refer to GB / T 38120 to measure the light transmittance ratio at 385 - 445 nm.

[0032] Example 1

[0033] A preparation method of a waterproof and fog-proof and radiation-proof lens, the preparation method of the waterproof and fog-proof and radiation-proof lens includes the following preparation steps:

[0034] (1) Immerse polycarbonate glass in an organosilicon hardening solution 5 times the mass of the polycarbonate glass. After standing for 3 min, cure at 80 °C for 46 min to obtain pretreated glass; place the pretreated glass in a container and introduce hydrogen at 130 cm 3 / min until the air pressure reaches 3×10 3 Pa, pretreat at 300 W for 13 min. Then, with the hydrogen flow rate unchanged, introduce methane and hydrogen at a flow rate ratio of 1:3 until the air pressure reaches 6×10 3 , deposit at 400 W for 66 min to obtain a nano-sheet carbon film glass;

[0035] (2) Place the nano-sheet carbon film glass in a container, evacuate to 1×10 -3 Pa, heat to 210 °C, and introduce nickel nitrate, hydrogen, and nitrogen at a flow rate ratio of 1:2:2. The hydrogen flow rate is 70 cm 3 / min. After introducing for 42 min, raise the temperature to 500 °C, introduce methane at 80 cm 3 / min until the air pressure reaches 28 Pa, react at 200 W for 41 min, and then cool to room temperature under a nitrogen atmosphere to obtain a composite carbon film glass;

[0036] (3) Place the composite carbon film glass in an electroplating solution that is 4 times the mass of the composite carbon film glass. Heat it to 50 °C, stir at 200 rpm, and apply double-pulse electroplating for 40 min under a 10 T magnetic field to obtain magnetic layer glass. The formula of the electroplating solution is as follows: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest is deionized water. The double-pulse electroplating parameters are: pulse frequency is 2 kHz, forward pulse current density is 9 A / dm 2 , the duty cycle is 0.42, and the reverse pulse current density is 1.5 A / dm 2 , and the duty cycle is 0.32;

[0037] (4) Using titanium dioxide as the target, place the magnetic layer glass at a distance of 40 mm. In an argon atmosphere, deposit for 31 min at a laser energy density of about 1.5 J / cm 2 , a repetition frequency of 5 Hz, and a pulse width of 20 ns to obtain radiation-proof layer glass;

[0038] (5) Mix the radiation-proof layer glass, hexamethylenediaminomethyltrimethoxysilane, absolute ethanol, and deionized water in a mass ratio of 1:0.5:8:2.5. React at 100 rpm for 68 min, then fish out and wash 4 times with deionized water to obtain preliminarily modified glass. Mix N,N-dimethylformamide, preliminarily modified glass, 2-amino-3-chloro-6-bromobenzoic acid, and potassium carbonate in a mass ratio of 38:1:0.8:0.5, heat to 50 °C, react for 12 h, then cool to room temperature, fish out, immerse in ice water that is 5 times the mass of the preliminarily modified glass, let stand for 28 min, filter, wash 3 times with deionized water, and dry at 50 °C for 8 h to obtain the lens precursor;

[0039] (6) Under nitrogen protection, mix the lens precursor, cinnamitrile, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate, cesium carbonate, and acetonitrile in a mass ratio of 1:0.8:0.8:0.03:3:5:19. React at 100 rpm and 110 °C for 13 h, then cool to room temperature, filter, wash 4 times with ethyl acetate, and dry at 40 °C for 6 h to obtain isatinone compound glass;

[0040] (7)Disperse the isatinone compound glass in acetonitrile which is 55 times the mass of the isatinone compound glass. Under a nitrogen atmosphere, cool it to 0 °C in an ice-water bath, then add tert-butyl hypochlorite which is 1.0 times the mass of the isatinone compound glass and (3S)-3-amino-N-cyclohexyl-2-oxohexanamide which is 0.8 times the mass of the isatinone compound glass. Let it rise to room temperature naturally. After reacting for 18 h, distill it at a vacuum of 0.01 MPa and 79 °C for 8 h. Then add isopropanol which is 8 times the mass of the isatinone compound glass. Stir at 100 rpm for 48 min, then filter, wash it 5 times with isopropanol, and dry it at 40 °C for 8 h to obtain the waterproof and radiation-proof lens.

[0041] Example 2

[0042] A preparation method of a waterproof and radiation-proof lens, the preparation method of the waterproof and radiation-proof lens comprising the following preparation steps:

[0043] (1) Immerse the polycarbonate glass in an organosilicon hardening solution which is 7.5 times the mass of the polycarbonate glass. After standing for 5 min, cure it at 85 °C for 38 min to obtain a pretreated glass; place the pretreated glass in a container and pass hydrogen into it at a rate of 165 cm 3 / min until the air pressure reaches 4×10 3 Pa. After pretreating it at 350 W for 10 min, keep the hydrogen flow rate unchanged, and pass methane and hydrogen into it at a flow rate ratio of 1:4 until the air pressure reaches 7.5×10 3 Pa. Deposit it at 450 W for 58 min to obtain a nano-sheet carbon film glass;

[0044] (2) Place the nano-sheet carbon film glass in a container, evacuate it to 3×10 -3 Pa, heat it to 250 °C, and pass nickel nitrate, hydrogen and nitrogen into it at a flow rate ratio of 1:3:3. The hydrogen flow rate is 85 cm 3 / min. After passing it for 36 min, raise the temperature to 525 °C, and pass methane into it at a rate of 100 cm 3 / min until the air pressure reaches 31 Pa. After reacting at 250 W for 35 min, cool it to room temperature under a nitrogen atmosphere to obtain a composite carbon film glass;

[0045] (3) Place the composite carbon film glass in an electroplating solution which is 7 times the mass of the composite carbon film glass. Heat it to 57 °C, stir it at 250 rpm and apply double-pulse electroplating for 31 min under a 13 T magnetic field to obtain a magnetic layer glass; the electroplating solution formula is: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest is deionized water; the double-pulse electroplating parameters are: the pulse frequency is 2 kHz, the forward pulse current density is 7 A / dm 2, with a duty cycle of 0.36 and a reverse pulse current density of 1.2 A / dm 2 , with a duty cycle of 0.25;

[0046] (4) Using titanium dioxide as the target, place the magnetic layer glass at a distance of 45 mm. In an argon atmosphere, the laser energy density is about 1.3 J / cm 2 , deposition is carried out for 25 min at a repetition frequency of 5 Hz and a pulse width of 23 ns to obtain the radiation-proof layer glass;

[0047] (5) Mix the radiation-proof layer glass, hexamethylenediaminomethyltrimethoxysilane, absolute ethanol, and deionized water in a mass ratio of 1:1:14.5:5. After reacting at 150 rpm for 59 min, fish out and wash 6 times with deionized water to obtain the preliminarily modified glass; Mix N,N-dimethylformamide, the preliminarily modified glass, 2-amino-3-chloro-6-bromobenzoic acid, and potassium carbonate in a mass ratio of 45:1:1.5:0.5, heat to 58 °C, react for 9 h, then cool to room temperature, fish out, immerse in ice water 8.5 times the mass of the preliminarily modified glass, let stand for 35 min, filter, wash 4 times with deionized water, and dry at 56 °C for 6 h to obtain the lens precursor;

[0048] (6) Under nitrogen protection, mix the lens precursor, cinnamonitrile, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytrispyrrolidinophosphonium hexafluorophosphate, cesium carbonate, and acetonitrile in a mass ratio of 1:1.2:1:0.03:5:7.5:22.5. After reacting at 150 rpm and 125 °C for 10.5 h, cool to room temperature, filter, wash 5 times with ethyl acetate, and dry at 46 °C for 4.5 h to obtain the isatinone compound glass;

[0049] (7) Disperse the isatinone compound glass in acetonitrile 59 times the mass of the isatinone compound glass. Under a nitrogen atmosphere, cool to 2 °C in an ice-water bath, then add tert-butyl hypochlorite 1.3 times the mass of the isatinone compound glass and (3S)-3-amino-N-cyclohexyl-2-oxohexanamide 1.1 times the mass of the isatinone compound glass. Let it rise to room temperature naturally, react for 21 h, then distill at a vacuum of 0.03 MPa and 82 °C for 10 h. Then add isopropanol 10.5 times the mass of the isatinone compound glass, stir at 150 rpm for 40 min, filter, wash 6 times with isopropanol, and dry at 50 °C for 6 h to obtain the waterproof and anti-radiation lens.

[0050] Example 3

[0051] A preparation method of a waterproof and anti-radiation lens, the preparation method of the waterproof and anti-radiation lens includes the following preparation steps:

[0052] (1) Immerse the polycarbonate glass in a silicone hardening solution that is 10 times the mass of the polycarbonate glass. After standing for 7 min, cure it at 90 °C for 30 min to obtain pretreated glass. Place the pretreated glass in a container and introduce hydrogen at a rate of 200 cm 3 / min until the pressure reaches 5×10 3 Pa. After pretreatment at 400 W for 7 min, keep the hydrogen flow rate unchanged and introduce methane and hydrogen at a flow rate ratio of 1:5 until the pressure reaches 9×10 3 Pa. Deposit for 50 min at 500 W to obtain nano-sheet carbon film glass;

[0053] (2) Place the nano-sheet carbon film glass in a container, evacuate to 5×10 -3 Pa, heat to 290 °C, and introduce nickel nitrate, hydrogen, and nitrogen at a flow rate ratio of 1:4:4. The hydrogen flow rate is 100 cm 3 / min. After introducing for 30 min, raise the temperature to 550 °C and introduce methane at a rate of 120 cm 3 / min until the pressure reaches 34 Pa. React at 300 W for 29 min, and then cool to room temperature under a nitrogen atmosphere to obtain composite carbon film glass;

[0054] (3) Place the composite carbon film glass in an electroplating solution that is 10 times the mass of the composite carbon film glass. Heat to 64 °C, stir at 300 rpm, and apply double-pulse electroplating for 22 min under a 16 T magnetic field to obtain magnetic layer glass. The electroplating solution formulation is: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest is deionized water. The double-pulse electroplating parameters are: pulse frequency is 2 kHz, forward pulse current density is 5 A / dm 2 , duty cycle is 0.30, reverse pulse current density is 0.9 A / dm 2 , duty cycle is 0.17;

[0055] (4) Using titanium dioxide as the target, place the magnetic layer glass at a distance of 50 mm. Deposit for 19 min in an argon atmosphere with a laser energy density of about 2.0 J / cm 2 , repetition frequency of 5 Hz, and pulse width of 25 ns to obtain radiation-proof layer glass;

[0056] (5) Mix the radiation-proof layer glass, hexamethylenediaminomethyltrimethoxysilane, absolute ethanol, and deionized water according to a mass ratio of 1:1.5:21:7.5. After reacting at 200 rpm for 50 min, fish out and wash with deionized water 8 times to obtain preliminarily modified glass. Mix N,N-dimethylformamide, preliminarily modified glass, 2-amino-3-chloro-6-bromobenzoic acid, and potassium carbonate according to a mass ratio of 52:1:2.1:0.5, heat to 66 °C, react for 6 h, cool to room temperature, fish out, immerse in ice water 12 times the mass of the preliminarily modified glass, let stand for 42 min, filter, wash with deionized water 5 times, and dry at 62 °C for 4 h to obtain the lens precursor.

[0057] (6) Under nitrogen protection, mix the lens precursor, phenylacetonitrile, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate, cesium carbonate, and acetonitrile according to a mass ratio of 1:1.6:1.3:0.03:7:10:26. After reacting at 200 rpm and 140 °C for 8 h, cool to room temperature, filter, wash with ethyl acetate 6 times, and dry at 53 °C for 3 h to obtain the isatinone compound glass.

[0058] (7) Disperse the isatinone compound glass in acetonitrile 63 times the mass of the isatinone compound glass. Under a nitrogen atmosphere, cool to 5 °C in an ice-water bath, then add tert-butyl hypochlorite 1.6 times the mass of the isatinone compound glass and (3S)-3-amino-N-cyclohexyl-2-oxohexanamide 1.4 times the mass of the isatinone compound glass. Let it rise to room temperature naturally and react for 24 h. Distill at a vacuum of 0.05 MPa and 85 °C for 12 h, then add isopropanol 13 times the mass of the isatinone compound glass. Stir at 200 rpm for 32 min, filter, wash with isopropanol 7 times, and dry at 60 °C for 4 h to obtain the waterproof and anti-radiation lens.

[0059] Comparative Example 1

[0060] A preparation method of a waterproof and anti-radiation lens, the preparation method of the waterproof and anti-radiation lens includes the following preparation steps:

[0061] (1) Immerse the polycarbonate glass in an organosilicon hardening solution 7.5 times the mass of the polycarbonate glass. Let stand for 5 min, then cure at 85 °C for 38 min to obtain pretreated glass. Place the pretreated glass in a container, evacuate to 3×10 -3 Pa, heat to 250 °C, and introduce nickel nitrate, hydrogen, and nitrogen according to a flow ratio of 1:3:3. The hydrogen flow rate is 85 cm 3 / min. After introducing for 36 min, heat to 525 °C, and at a rate of 100 cm 3Methane was introduced until the pressure reached 31 Pa. After reacting for 35 min at 250 W, it was cooled to room temperature under a nitrogen atmosphere to obtain a composite carbon film glass.

[0062] (2) The composite carbon film glass was placed in an electroplating solution that was 7 times the mass of the composite carbon film glass. It was heated to 57 °C, stirred at 250 rpm, and under a 13 T magnetic field, double-pulse electroplating was carried out for 31 min to obtain a magnetic layer glass; the electroplating solution formula was: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest was deionized water; the double-pulse electroplating parameters were: pulse frequency was 2 kHz, forward pulse current density was 7 A / dm 2 , duty cycle was 0.36, reverse pulse current density was 1.2 A / dm 2 , duty cycle was 0.25;

[0063] (3) Using titanium dioxide as the target, the magnetic layer glass was placed at a distance of 45 mm. In an argon atmosphere, the laser energy density was about 1.3 J / cm 2 , repetition frequency was 5 Hz, pulse width was 23 ns, and deposition was carried out for 25 min to obtain a radiation protection layer glass;

[0064] (4) The radiation protection layer glass, hexamethylenediamine methyltrimethoxysilane, absolute ethanol, and deionized water were mixed in a mass ratio of 1:1:14.5:5. After reacting for 59 min at 150 rpm, it was fished out and washed 6 times with deionized water to obtain a preliminarily modified glass; N,N-dimethylformamide, the preliminarily modified glass, 2-amino-3-chloro-6-bromobenzoic acid, and potassium carbonate were mixed in a mass ratio of 45:1:1.5:0.5, heated to 58 °C, reacted for 9 h, cooled to room temperature, fished out, immersed in ice water that was 8.5 times the mass of the preliminarily modified glass, left standing for 35 min, filtered, washed 4 times with deionized water, and dried at 56 °C for 6 h to obtain a lens precursor;

[0065] (5) Under nitrogen protection, the lens precursor, cinnamitrile, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytrispyrrolidinophosphonium hexafluorophosphate, cesium carbonate, and acetonitrile were mixed in a mass ratio of 1:1.2:1:0.03:5:7.5:22.5. After reacting for 10.5 h at 150 rpm and 125 °C, it was cooled to room temperature, filtered, washed 5 times with ethyl acetate, and dried at 46 °C for 4.5 h to obtain an isatinone compound glass;

[0066] (6)Disperse the isatinone compound glass in acetonitrile which is 59 times the mass of the isatinone compound glass. Under a nitrogen atmosphere, cool it to 2 °C in an ice-water bath, then add tert-butyl hypochlorite which is 1.3 times the mass of the isatinone compound glass and (3S)-3-amino-N-cyclohexyl-2-oxohexanamide which is 1.1 times the mass of the isatinone compound glass. Let it naturally rise to room temperature. After reacting for 21 h, distill it at a vacuum of 0.03 MPa and 82 °C for 10 h. Then add isopropanol which is 10.5 times the mass of the isatinone compound glass, stir at 150 rpm for 40 min, filter, wash it 6 times with isopropanol, and dry it at 50 °C for 6 h to obtain a waterproof and radiation-proof lens.

[0067] Comparative Example 2

[0068] The difference between Comparative Example 2 and Example 2 is that step (2) is absent, and step (3) is changed to: Place the nanosheet carbon film glass in an electroplating solution which is 7 times the nanosheet carbon film glass, heat it to 57 °C, stir at 250 rpm and under a 13 T magnetic field, and perform double-pulse electroplating for 31 min to obtain a magnetic layer glass; the formula of the electroplating solution is: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecylsulfonate 0.05 g / L, and the rest is deionized water; the double-pulse electroplating parameters are: the pulse frequency is 2 kHz, the forward pulse current density is 7 A / dm 2 , the duty cycle is 0.36, the reverse pulse current density is 1.2 A / dm 2 , and the duty cycle is 0.25. The remaining preparation steps are the same as those in Example 2.

[0069] Comparative Example 3

[0070] The difference between Comparative Example 3 and Example 2 is that step (3) is absent, and step (4) is changed to: Using titanium dioxide as the target, place the composite carbon film glass at a distance of 45 mm. In an argon atmosphere, deposit for 25 min at a laser energy density of about 1.3 J / cm 2 , a repetition frequency of 5 Hz, and a pulse width of 23 ns to obtain a radiation-proof layer glass. The remaining preparation steps are the same as those in Example 2.

[0071] Comparative Example 4

[0072] The difference between Comparative Example 4 and Example 2 is that step (4) is absent, and step (3) is changed to: placing the composite carbon film glass in an electroplating solution 7 times the mass of the composite carbon film glass, heating to 57 °C, stirring at 250 rpm and applying double-pulse electroplating for 31 min under a 13 T magnetic field to obtain radiation-proof layer glass; the formula of the electroplating solution is: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest is deionized water; the double-pulse electroplating parameters are: pulse frequency is 2 kHz, forward pulse current density is 7 A / dm 2 , duty cycle is 0.36, reverse pulse current density is 1.2 A / dm 2 , duty cycle is 0.25. The remaining preparation steps are the same as those in Example 2.

[0073] Comparative Example 5

[0074] The difference between Comparative Example 5 and Example 2 lies in the difference in step (5). Step (5) is changed to: mixing the radiation-proof layer glass, hexamethylenediaminomethyltrimethoxysilane, absolute ethanol and deionized water in a mass ratio of 1:1:14.5:5, reacting at 150 rpm for 59 min, fishing out, and washing 6 times with deionized water to obtain the lens precursor. The remaining preparation steps are the same as those in Example 2.

[0075] Comparative Example 6

[0076] The difference between Comparative Example 6 and Example 2 lies in the difference in step (6). Step (6) is changed to: under nitrogen protection, mixing the lens precursor, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate, cesium carbonate and acetonitrile in a mass ratio of 1:1:0.03:5:7.5:22.5, reacting at 150 rpm and 125 °C for 10.5 h, cooling to room temperature, filtering, washing 5 times with ethyl acetate, and drying at 46 °C for 4.5 h to obtain isatinone compound glass. The remaining preparation steps are the same as those in Example 2.

[0077] Comparative Example 7

[0078] The difference between Comparative Example 7 and Example 2 is that step (7) is absent, and the remaining preparation steps are the same as those in Example 2.

[0079] Effect Example

[0080] Table 1 below gives the performance analysis results of the waterproof and radiation-proof lenses of Examples 1 to 3 and Comparative Examples 1 to 7 of the present invention.

[0081] Table 1

[0082]

[0083] From the comparison of the experimental data of the water mist dissipation time and the water mist condensation situation after irradiation between the examples and the comparative examples, it can be found that for the anti-radiation layer prepared by the present invention, by sequentially depositing a conductive layer, a magnetic layer, and a non-magnetic layer, the existence of multiple interfaces accelerates the conversion of electromagnetic waves into heat energy, improves the water mist resistance of the lens. At the same time, the non-magnetic layer uses titanium dioxide as the raw material, which can further improve the water mist resistance of the lens; from the comparison of the shielding rate experimental data between the examples and the comparative examples, it can be found that the present invention sequentially deposits a carbon film and vertically grown carbon nanotubes to form a conductive network in series, forming a conductive loss to improve the anti-radiation ability of the lens, then deposits a magnetic layer to form a magnetic loss, and then coats non-magnetic titanium dioxide to generate magnetic coupling between magnetic particles to form a magnetic absorption network, promoting the magnetic loss of electromagnetic radiation and improving the anti-radiation ability of the lens; in addition, the existence of multiple interfaces and the resonance generated by magnetic particles act together on electromagnetic waves, enabling the lens to have a strong electromagnetic radiation attenuation ability and improving the anti-radiation property of the lens; from the comparison of the transmittance experimental data between the examples and the comparative examples, after using the aminated modified anti-radiation layer, it is successively grafted with 2-amino-3-chloro-6-bromobenzoic acid, cinnamitrile, and dimethylaminopropylamine on the surface to form a ring to form an isoindolinone compound, which effectively absorbs blue light and makes the lens have an anti-blue light effect; then reacting with (3S)-3-amino-N-cyclohexyl-2-oxohexanamide to generate an azo group, which acts together to improve the anti-blue light property of the lens.

[0084] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claimed claim.

Claims

1. A waterproof and fog-proof and radiation-proof lens, characterized in that, The waterproof and anti-radiation lens is prepared by the following method: the resin glass is hardened to obtain pretreated resin glass; then, through the first deposition treatment, the second deposition treatment, the third deposition treatment, and sputtering deposition treatment, an anti-radiation layer glass is formed, and then modified treatment is carried out; The first deposition treatment is to place the pretreated resin glass in a mixed atmosphere of methane and hydrogen, and obtain nano-sheet carbon film glass by microwave plasma; the second deposition treatment is to place the nano-sheet carbon film glass in a mixed atmosphere of nickel nitrate, nitrogen, and hydrogen, and after reacting for a predetermined time, introduce methane, and prepare composite carbon film glass by microwave plasma; the third deposition treatment is to place the composite carbon film glass in an electroplating solution, and under magnetic stirring, apply double-pulse electroplating to obtain magnetic layer glass; the sputtering deposition treatment is to use titanium dioxide as a target and perform pulsed laser deposition; Mix the anti-radiation layer glass with hexamethylenediamine methyltrimethoxysilane solution, stir and react to obtain preliminarily modified glass; then mix the preliminarily modified glass with 2-amino-3-chloro-6-bromobenzoic acid, heat and react to a predetermined time, then cool, fish out, soak in ice water, stand, filter, wash, and dry to obtain a lens precursor; then mix the lens precursor, cinnamonitrile, and dimethylaminopropylamine, stir and heat and react for a period of time, then cool, filter, and wash to obtain isatinone compound glass; then mix the isatinone compound glass with (3S)-3-amino-N-cyclohexyl-2-oxohexanamide, react at room temperature for a period of time, distill, then add isopropanol, stir, filter, wash, and dry.

2. The waterproof and anti-fogging and anti-radiation lens according to claim 1, wherein, The resin glass is one of allyl diglycol carbonate glass, acrylic glass, polyurethane glass, or polycarbonate glass.

3. A preparation method of a waterproof, fog-proof and radiation-proof lens, characterized in that, It includes the following preparation steps: (1) Place the pretreated resin glass in a container, introduce hydrogen until the air pressure reaches 3×10 3 ~5×10 3 Pa, after pretreatment for 7 - 13 minutes under 300 - 400 W, introduce methane and hydrogen until the air pressure reaches 6×10 3 ~9×10 3 Pa, deposit for 50 - 66 minutes under 400 - 500 W to obtain the nano - sheet carbon film glass; (2)Place the carbon film glass nanosheets in a container, evacuate to 1×10 -3 ~5×10 -3 Pa, heat to 210~290 °C, introduce nickel nitrate, hydrogen and nitrogen. After introducing for 30~42 min, raise the temperature to 500~550 °C, and introduce methane at 80~120 cm 3 / min until the pressure is 28~34 Pa. After reacting at 200~300 W for 29~41 min, cool to room temperature under a nitrogen atmosphere to obtain the composite carbon film glass; (3) Place the composite carbon film glass in an electroplating solution that is 4 to 10 times the mass of the composite carbon film glass, heat to 50 to 64 °C, stir at 200 to 300 rpm, and apply double-pulse electroplating for 22 to 40 min under a magnetic field of 10 to 16 T to obtain magnetic layer glass; (4) Using titanium dioxide as the target, place the magnetic layer glass at a distance of 40 - 50 mm. In an argon atmosphere, deposit for 19 - 31 minutes under a laser energy density of 1.5 - 2.0 J / cm 2 , a repetition frequency of 5 Hz, and a pulse width of 20 - 25 ns to obtain the radiation - resistant layer glass; (5) Mix the anti-radiation layer glass, hexamethylenediamine methyltrimethoxysilane, absolute ethanol, and deionized water according to a mass ratio of 1:0.5:8:2.5 to 1:1.5:21:7.5, react at 100 to 200 rpm for 50 to 68 min, then fish out, wash with deionized water 4 to 8 times to obtain preliminarily modified glass; mix N,N-dimethylformamide, preliminarily modified glass, 2-amino-3-chloro-6-bromobenzoic acid, and potassium carbonate according to a mass ratio of 38:1:0.8:0.5 to 52:1:2.1:0.5, heat to 50 to 66 °C, react for 6 to 12 h, then cool to room temperature, fish out, soak in ice water that is 5 to 12 times the mass of the preliminarily modified glass, stand for 28 to 42 min, then filter, wash with deionized water 3 to 5 times, and dry at 50 to 62 °C for 4 to 8 h to obtain a lens precursor; Under nitrogen protection, the lens precursor, cinnamitrile, dimethylaminopropylamine, copper chloride, 1H-benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate, cesium carbonate, and acetonitrile were mixed at a mass ratio of 1:0.8:0.8:0.03:3:5:19 to 1:1.6:1.3:0.03:7:10:

26. After reacting at 100 - 200 rpm and 110 - 140 °C for 8 - 13 h, it was cooled to room temperature, filtered, washed with ethyl acetate 4 - 6 times, and then dried at 40 - 53 °C for 3 - 6 h to obtain the isatinone compound glass. (7) The isatinone compound glass was dispersed in acetonitrile at 55 - 63 times the mass of the isatinone compound glass. Under a nitrogen atmosphere, it was cooled to 0 - 5 °C in an ice-water bath, then tert-butyl hypochlorite at 1.0 - 1.6 times the mass of the isatinone compound glass and (3S)-3-amino-N-cyclohexyl-2-oxohexanamide at 0.8 - 1.4 times the mass of the isatinone compound glass were added. It was allowed to rise to room temperature naturally and reacted for 18 - 24 h. Then, it was distilled at a vacuum of 0.01 - 0.05 MPa and 79 - 85 °C for 8 - 12 h. Then, isopropanol at 8 - 13 times the mass of the isatinone compound glass was added, and it was stirred at 100 - 200 rpm for 32 - 48 min, filtered, washed with isopropanol 5 - 7 times, and dried at 40 - 60 °C for 4 - 8 h to obtain the waterproof and radiation-proof lens.

4. The preparation method of a waterproof and anti-radiation lens according to claim 3, characterized in that The preparation method of the pretreated resin glass in step (1) is as follows: The resin glass was immersed in an organosilicon hardening solution at 5 - 10 times the mass of the resin glass, allowed to stand for 3 - 7 min, and then cured at 80 - 90 °C for 30 - 46 min.

5. The preparation method of a waterproof and anti-radiation lens according to claim 3, characterized in that, The hydrogen flow rate in step (1) is 130~200 cm 3 / min; methane and hydrogen are introduced at a flow rate ratio of 1:3~1:

5.

6. The preparation method of a waterproof and anti-radiation lens according to claim 3, characterized in that, In step (2), nickel nitrate, hydrogen, and nitrogen are introduced at a flow rate ratio of 1:2:2 to 1:4:4, and the hydrogen flow rate is 70 to 100 cm 3 / min.

7. The preparation method of a waterproof and anti-fogging and anti-radiation lens according to claim 3, characterized in that, The electroplating solution formulation in step (3) is as follows: nickel sulfate heptahydrate 180 g / L, nickel chloride hexahydrate 20 g / L, ferrous sulfate heptahydrate 10 g / L, sodium chloride 20 g / L, trisodium citrate dihydrate 20 g / L, boric acid 40 g / L, sodium dodecyl sulfonate 0.05 g / L, and the rest is deionized water.

8. The preparation method of a waterproof and anti-radiation lens according to claim 3, characterized in that, The dual-pulse electroplating parameters described in step (3) are: the pulse frequency is 2 kHz, the forward pulse current density is 5 - 9 A / dm 2 , the duty cycle is 0.30 - 0.42, and the reverse pulse current density is 0.9 - 1.5 A / dm 2 , and the duty cycle is 0.17 - 0.32.

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