WO2024093106A1 - Clear-base-color, blue-light-blocking and anti-infrared resin lens and preparation method therefor - Google Patents

Abstract

Provided in the present invention are a clear-base-color, blue-light-blocking, anti-infrared and high-temperature-resistant resin lens and a preparation method therefor. The resin lens comprises: a resin lens substrate, a hardening layer, a clear-base-color anti-infrared film layer and a waterproof layer, wherein the substrate, the hardening layer and the clear-base-color anti-infrared film layer are arranged in sequence, the hardening layer is located on the surface of the resin lens substrate, and the clear-base-color anti-infrared film layer is located on the surface of the hardening layer; and the clear-base-color anti-infrared film layer is composed of a high-refractive-index material, i.e. titanium-niobium composite oxide, a low-refractive-index material, i.e. silicon-aluminum composite oxide, and an absorbing material, i.e. titanium nitride. In the present invention, by adjusting the structure of the clear-base-color anti-infrared film layer and using a special titanium nitride plating process, an anti-infrared lens having a good visual effect is obtained while anti-reflection and blue light blocking functions are achieved, the high-temperature resistance and environmental resistance of the resin lens are greatly improved, and the resin lens has good market application prospects.

Description

A clear-background-color blue-light-proof and infrared-proof resin lens and a preparation method thereof Technical Field

The present invention relates to the technical field of resin lens preparation, and in particular to a clear-bottom-color, blue-light-proof, infrared-proof, and high-temperature-resistant resin lens and a preparation method thereof.

Background technique

In recent years, the demand for optical resin lenses in the domestic and international eyewear markets has been growing. Compared with glass lenses, resin lenses have the advantages of light weight, good dyeing performance, and easy processing. Medium and high refractive index optical resin lenses are favored by users for their unique advantages such as high light transmittance, UV protection, and ultra-thinness.

In order to meet the requirements of the optical performance of resin lenses, a film is generally coated on the surface of the resin lens to reduce the reflection of light and enhance the transmission of light, which is an optical anti-reflection film. Near-infrared is not sensitive to the human eye and is mainly absorbed by the cornea, which has potential damage to the human eye. This requires that the optical film layer has the characteristics of anti-reflection and infrared protection. Such an optical film layer is much thicker than a general conventional film layer. In addition, since the main material of the optical film is an inorganic material, and the polymer resin lens substrate is an organic material, the difference in the physical and chemical properties of the two leads to higher stress in the lens after coating, which in turn leads to poor temperature resistance and durability. In particular, the film layer with a clear background color and infrared protection function is generally thicker, and its effect on the stress of the lens after coating is particularly significant, which affects its normal use. Therefore, how to provide a low-reflection, infrared-proof, high-temperature-resistant and durable resin lens has become an urgent problem to be solved in this field.

Blue light protection can effectively protect consumers from the demands of electronic use environments. The new national blue light protection standard also distinguishes between harmful blue light and beneficial blue light. However, blue light protection usually makes the lenses more yellow and less bright. In order to meet the new demands of consumers in the new electronic environment, we urgently need to provide a blue light protection resin lens with a clear base color.

Therefore, we need to provide new resin lens products that comprehensively meet the performance and protection requirements of anti-reflection, blue light protection, infrared protection, and the aesthetic requirements of clear background color.

Summary of the invention

In order to overcome the defects of the prior art, the present invention aims to provide a clear background color, blue light protection, infrared protection and high temperature resistant resin lens and a preparation method thereof, which can effectively meet the anti-reflection requirements, achieve good infrared protection effect, improve the high temperature resistance and durability of the resin lens by reducing stress, and use special processes to plate special materials to meet the national blue light protection standards and clear background color visual effects.

The present invention is achieved through the following technical solutions:

The first aspect of the present invention provides a clear base color, blue light proof, infrared proof and high temperature resistant resin lens, comprising: a resin lens substrate, a hardened layer and a clear base color infrared proof layer; wherein the resin lens substrate, the hardened layer and the clear base color infrared proof film layer are arranged in sequence, the hardened layer is located on the surface of the resin lens substrate, and the clear base color infrared proof film layer is located on the surface of the hardened layer;

The UV cut-off wavelength of the resin lens substrate is 405-407nm;

Furthermore, the clear base color infrared-proof and high temperature-resistant resin lens further comprises a waterproof layer, and the waterproof layer is located on the surface of the clear base color infrared-proof film layer;

Furthermore, the material of the hardened layer is organic silicon; further preferably, the organic silicon contains at least Ti element;

Further, the clear background color anti-infrared film layer includes a silicon-aluminum composite oxide layer, a titanium-niobium composite oxide layer, a tin-doped indium oxide (i.e., ITO) layer, and a titanium nitride (TiN) layer; further, the clear background color anti-infrared film layer includes three layers of silicon-aluminum composite oxide layers, three layers of titanium-niobium composite oxide layers, a layer of tin-doped indium oxide (i.e., ITO) layer, a layer of silicon dioxide, and a layer of titanium nitride (TiN);

Further, the silicon-aluminum composite oxide layer is composed of a composite material of SiO ₂ and Al ₂ O ₃ , wherein the molar fraction of SiO ₂ in the composite material is 70% to 95%; further preferably, wherein the molar fraction of SiO ₂ in the composite material is 92%;

Further, the titanium-niobium composite oxide layer is composed of a composite material of TiO ₂ and Nb ₂ O ₅ , wherein TiO ₂ accounts for 10% to 90% of the molar fraction of the composite material; preferably, wherein TiO ₂ accounts for 80% of the molar fraction of the composite material;

Furthermore, the purity of TiN in the titanium nitride layer is greater than 99.9%;

Furthermore, the thickness of the hardened layer is 1 to 5 μm;

Furthermore, the thickness of the clear base color anti-infrared film layer is 290 to 950 nm;

Furthermore, the thickness of the waterproof layer is 4 to 20 nm;

Furthermore, the average reflectivity of the clear-base-color blue-light-proof and infrared-proof resin high-temperature-resistant lens is ≤1.5%;

Furthermore, the near infrared blocking rate of the clear base color anti-blue light and anti-infrared resin high temperature resistant lens is greater than 55%;

Furthermore, the yellow index of the clear base color anti-blue light and anti-infrared resin high temperature resistant lens is ≤4.5%;

The second aspect of the present invention provides a method for preparing the above-mentioned clear base color blue light and infrared resistant resin high temperature resistant lens, comprising the following steps:

S1: preparing a hard layer: forming a hard layer on the surface of a resin lens substrate, that is, obtaining a resin lens containing a hard layer;

S2 preparing a clear background color infrared-proof film layer: forming the clear background color infrared-proof film layer on the surface of the resin lens obtained in S1, that is, obtaining a resin lens containing a clear background color infrared-proof film layer, specifically comprising:

S21: forming a resin lens having a first silicon-aluminum composite oxide layer and a second titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S1;

S22: forming a third layer of a resin lens containing a titanium nitride layer on the surface of the resin lens obtained in step S21;

S23: forming a fourth _SiO2- containing resin lens on the surface of the resin lens obtained in step S22;

S24: forming a fifth titanium-niobium composite oxide layer, a sixth silicon-aluminum composite oxide layer, and a seventh titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S23;

S25: forming an eighth ITO-containing resin lens on the surface of the resin lens obtained in step S24;

S26: forming a ninth layer of a resin lens containing a silicon-aluminum composite oxide layer on the surface of the resin lens obtained in step S25;

S3: preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in step S2.

Beneficial Effects

1. The present invention adopts a specific UV405 resin lens substrate to make the lens close to the blue light protection standard and maintain a low yellow index;

2. The present invention adopts a specific film layer to make the lens have the effects of infrared protection, blue light protection and clear background color, which specifically includes: (1) The film layer is prepared by using titanium niobium composite oxide material to have infrared protection effect, improve the temperature resistance and durability of the product, and improve the repeatability and mass production of the product, and significantly improve the temperature resistance and durability of the lens: a. _TiO2 doped with a certain _molar ratio of _Nb2O5 can effectively avoid the easy crystallization characteristics of the _TiO2 film layer, and can also effectively avoid the defect of the dense _{Nb2O5 film} layer being easy to crack on the resin lens. Under the condition of low ion source energy for coating the resin glasses, the film layer is ensured to be in an amorphous state to prevent the film layer from cracking due to crystallization, thereby improving the high temperature and high humidity resistance of the film layer and the lens, and further improving the durability of the product; b. In addition, when preparing the low-reflection titanium niobium composite oxide film layer, since the film layer material is doped with _TiO2 and _Nb2O5 , the _influence of _TiO2 on O in the IAD auxiliary process is reduced. _2. The sensitivity of the flow rate is reduced, the process difficulty is reduced and the repeatability and mass production of the product are effectively improved: c. The film material adopts a composite material of TiO ₂ and Nb ₂ O ₅ , and the optical refractive index is close to TiO ₂ , which is higher than the refractive index of materials such as Nb ₂ O ₅ , so that the anti-infrared cutoff effect is better, the reflectivity of the anti-reflection film is lower, and the infrared cutoff is deeper than other existing products, and the light transmittance of the resin lens is improved, so that the lens prepared by the present invention has a good visual effect while protecting the human eye and reducing near-infrared radiation;

(2) The TiN layer prepared by a specific process can supplement the anti-blue light standard, enhance infrared blocking, and reduce the yellow index to increase the effect of clearing the background color. The film layer produces 2% absorption on one side of the 415-445nm band, which is important for the anti-blue light standard, to ensure that the lens meets the anti-blue light standard and protect the human eye from blue light damage; the absorption of yellow light is about 0.6% higher than that of blue light, thereby effectively reducing the yellow index and ensuring that the lens is clear and white; the absorption of near-infrared is above 3%, which effectively increases the infrared blocking rate and reduces the damage of infrared to the human eye;

(3) Improving the high temperature resistance of the product: The present invention uses a silicon-aluminum composite oxide layer and a SiO2 layer in combination, which effectively avoids the formation of long columns by SiO2, resulting in high stress in the film layer, maintains the glassy structure of the film layer, and improves the high temperature resistance of the film layer.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic diagram of the layers of a clear base color infrared-proof resin lens prepared in Examples 1 to 4 of the present invention; a resin lens substrate 1, a hardened layer 2, a clear base color infrared-proof film layer 3, and a waterproof layer 4; wherein the clear base color infrared-proof film layer 3 includes: a silicon-aluminum composite oxide layer 3-1, a titanium-niobium composite oxide layer 3-2, a titanium nitride layer 3-3 plated by a special process, a silicon dioxide layer 3-4, a titanium-niobium composite oxide layer 3-5, a silicon-aluminum composite oxide layer 3-6, a titanium-niobium composite oxide layer 3-7, an ITO layer 3-8, and a silicon-aluminum composite oxide layer 3-9

Detailed ways

In a specific embodiment, the clear background color infrared protection film layer includes three silicon aluminum composite oxide layers, three titanium niobium composite oxide layers, a titanium nitride layer, a silicon dioxide layer and a tin-doped indium oxide (i.e., ITO) layer, wherein the clear background color infrared protection film layer includes the following layers in order: (1) silicon aluminum composite oxide layer, (2) titanium niobium composite oxide layer, (3) titanium nitride layer, (4) silicon dioxide layer, (5) titanium niobium composite oxide layer, (6) silicon aluminum composite oxide layer, (7) titanium niobium composite oxide layer, (8) tin-doped indium oxide (i.e., ITO) layer, and (9) silicon aluminum composite oxide layer; and the first silicon aluminum composite oxide layer is located on the surface of the hardened layer;

Furthermore, in a specific embodiment, the thickness of each layer of the clear base color anti-infrared film layer is:

The thickness of the first silicon-aluminum composite oxide layer is 0 to 180 nm, preferably 5 to 30 nm;

The thickness of the second titanium-niobium composite oxide layer is 10 to 40 nm, preferably 10 to 20 nm;

The thickness of the third titanium nitride layer is 0.5 to 2 nm, preferably 0.7 to 1.2 nm;

The thickness of the fourth silicon dioxide layer is 20 to 60 nm, preferably 30 to 50 nm;

The thickness of the fifth titanium-niobium composite oxide layer is 80 to 150 nm, preferably 100 to 120 nm;

The thickness of the sixth silicon-aluminum composite oxide layer is 90 to 250 nm, preferably 140 to 200 nm;

The thickness of the seventh titanium-niobium composite oxide layer is 80 to 150 nm, preferably 90 to 110 nm;

The thickness of the eighth ITO layer is 2 to 10 nm, preferably 5 nm;

The thickness of the ninth silicon-aluminum composite oxide layer is 60 to 130 nm, preferably 65 to 90 nm;

In a specific embodiment, the step of preparing the hardened layer in S1 comprises: immersing the ultrasonically cleaned resin lens substrate into a 25-30% by weight hardening solution aqueous solution at a dipping temperature of 10-20° C., dipping for 4-8 seconds and then pulling out the solution at a speed of 1.0-3.0 mm/s, and then drying it at 70-90° C. for 2-5 hours, then taking out the substrate and sending it to a drying oven for drying and curing, the curing temperature is 100-150° C., and the curing time is 120-180 min, to obtain a resin lens containing a hardened layer;

In a specific embodiment, the process of preparing the clear base color infrared protection film layer in step S2 comprises:

In a vacuum coating machine, a vacuum coating process is adopted to evaporate silicon-aluminum composite oxide layer, titanium-niobium composite oxide, titanium nitride, silicon dioxide and ITO solid film layer materials, and then transmit them through the gas phase to deposit them into a thin film on the surface of the resin lens obtained in step S1 to form a clear base color anti-infrared film layer, which specifically includes the following steps:

S21: forming a first layer of silicon-aluminum composite oxide on the surface of the resin lens obtained in step S1, heating the silicon-aluminum composite oxide with a high-energy electron beam at a rate of 1000 Å under the conditions of a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 50-70°C, and an ion source-assisted process. Depositing the evaporated silicon-aluminum composite oxide in the form of nano-scale molecules to obtain a resin lens containing a first silicon-aluminum composite oxide layer;

S22: forming ^a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S21, heating the titanium-niobium composite oxide on the surface of the resin lens obtained in step S21 by using a high-energy electron beam at a rate of depositing the evaporated titanium-niobium composite oxide in the form of nano-scale molecules to obtain a resin lens containing a second titanium-niobium composite oxide layer;

S23: forming a titanium nitride layer on the surface of the resin lens obtained in step S22, specifically comprising:

S231: first evacuate to a background vacuum degree of ≤8×10 ^-4 Pa, then bombard with an ion source Hall source for 50 to 80 seconds, the ion source bombardment parameters are: anode voltage: 90 to 140 V, anode current: 2.5 to 5 A, auxiliary gas is Ar, and the flow rate is 5 to 20 sccm; preferably, the ion source Hall source bombardment time is 60 seconds, and the ion source bombardment parameters are: anode voltage: 110 V, anode current: 3 A, auxiliary gas is Ar, and the flow rate is 10 sccm;

S232: Deposition in an ion source assisted process, using a high energy electron beam to heat TiN at a rate The evaporated TiN is deposited in the form of nano-scale molecules. The auxiliary parameters of the ion source are: anode voltage: 90-140V, anode current: 2.5-5A, auxiliary gas is Ar and _N2 , Ar flow rate is 5-15sccm, _N2 flow rate is: 3-15sccm; preferably, under the assistance of the ion source, at a rate The evaporated TiN is deposited in the form of nano-scale molecules, and the auxiliary parameters of the ion source are: anode voltage: 110V, anode current: 3A, auxiliary gas is Ar and _N2 , Ar flow rate is 10sccm, _N2 flow rate is: 5sccm;

S233: continue bombarding the TiN film surface with the ion source Hall source for 20 to 40 seconds, the bombardment parameters are: anode voltage: 90 to 140 V, anode current: 2.5 to 5 A, auxiliary gas is Ar and N ₂ , Ar flow rate is 5 to 15 sccm, N ₂ flow rate is 3 to 15 sccm; preferably, the bombardment time is 30 seconds, the bombardment parameters are: anode voltage: 110 V, anode current: 3 A, auxiliary gas is Ar and N ₂ , Ar flow rate is 10 sccm, N ₂ flow rate is 5 sccm;

S24: The surface of the resin lens obtained in S23 is heated by a high-energy electron beam at a rate of 10000 t/ _cm2 , with a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 50-70°C, and an ion source assisted process. The evaporated _SiO2 is deposited in the form of nano-scale molecules to obtain a resin lens containing a _SiO2 layer; the ion source auxiliary parameters are: anode voltage: 90-140V, anode current: 2.5-5A, auxiliary gas is Ar, and the flow rate is 5-20sccm; preferably, the ion source is assisted at a rate of The evaporated SiO ₂ was deposited in the form of nano-scale molecules, and the ion source bombardment auxiliary parameters were: anode voltage: 110 V, anode current: 3 A, auxiliary gas was Ar, and the flow rate was 10 sccm;

S25: repeating step S22 to form a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S24;

S26: repeat step S21 to form a silicon-aluminum composite oxide layer on the surface of the resin lens obtained in step S25;

S27: repeat step S22 to form a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S26;

S28: The surface of the resin lens obtained in S27 is heated by a high-energy electron beam at a rate of 1000 Å to 1000 Å under the conditions that the background vacuum is ≤3×10 ^-3 Pa, the temperature in the coating chamber is 50-70°C, and an ion source is used to assist the process. Depositing the evaporated ITO in the form of nano-scale molecules to obtain a resin lens containing an ITO layer;

S29: continuing to use the vacuum coating process on the surface of the resin lens obtained in S28, repeating the process steps of S21, and forming another layer of the resin lens containing the silicon-aluminum composite oxide layer;

In steps S21, S22, S25 to S29, the ion source assisted deposition process parameters are: the ion source is a Hall source, the anode voltage is 90 to 140 V, the anode current is 2.5 to 5 A, the auxiliary gas is O ₂ , and the flow rate is 10 to 30 sccm; preferably, the ion source assisted deposition process parameters are: the ion source is a Hall source, the anode voltage is 110 V, the anode current is 3 A, the auxiliary gas is O ₂ , and the flow rate is 15 sccm;

In a specific embodiment, the step S3: forming a waterproof layer on the surface of the resin lens obtained in step S2 comprises the following steps: continuing to use a vacuum coating process on the surface of the lens obtained in step S29, using a high-energy electron beam to heat the material at a rate of 1000 ℃ under the conditions that the background vacuum degree is ≤3×10 ^-3 Pa and the temperature in the coating chamber is 50-70°C. Depositing the evaporated fluorine-containing waterproof material (preferably a waterproof material containing perfluoroalkane (C ₁₂ F ₂₇ N)) in the form of nano-scale molecules to obtain a resin lens containing a waterproof layer;

In a specific embodiment, the titanium nitride material has a molecular formula of TiN and a purity of 99.9%, and is made by sintering titanium nitride powder using a conventional process, and is specifically commissioned to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. for development and production;

In a specific embodiment, the silicon-aluminum composite oxide is developed and produced by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. The silicon-aluminum composite oxide layer is composed of a composite material of SiO ₂ and Al ₂ O ₃ , and the molar fraction of SiO ₂ in the composite material is 70% to 95%. For specific models, please refer to the embodiments and comparative examples;

In a specific embodiment, the titanium-niobium composite oxide is developed and produced by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. The titanium-niobium composite oxide is composed of TiO ₂ and Nb ₂ O ₅ , wherein the molar fraction of TiO ₂ is 10% to 90%. For specific models, please refer to the examples and comparative examples;

The resin lens substrate selected in the present invention is a conventional lens in the art, and the content of the UV powder is adjusted so that the UV cut-off wavelength is 405-407 nm. The definition of the UV cut-off wavelength refers to 5.4.2.4.4 of the optical resin lens standard QB/T 2506-2017;

For example, in a specific embodiment, a resin lens substrate with model MR-8 (refractive index 1.60) or MR-7 (refractive index 1.67) and a UV cutoff wavelength of 405 to 407 nm is purchased from Mitsui Chemicals, Inc. of Japan, hereinafter referred to as "MR-8-UV405" or "MR-7-UV405"; or in a specific embodiment, a resin lens substrate with a refractive index of 1.56 and a UV cutoff wavelength of 405 to 407 nm developed and produced by Jiangsu Shike New Materials Co., Ltd. is purchased, hereinafter referred to as "SK1.56-UV405". For the specific preparation method of the resin lens substrate, refer to the patent of Shike Optics Co., Ltd.: CN201410245692.6.

The present invention can select a conventional hardening liquid. For example, in a specific embodiment, the hardening liquid model Z117 or Z118 (hereinafter referred to as "Z117" or "Z118") of Ito Optical Industry Co., Ltd. is selected; or in a specific embodiment, the hardening liquid model VH56 (hereinafter referred to as "VH56") of Dun Optics (Changshu) Co., Ltd. is selected. Selecting the hardening liquid for coating greatly improves the dense connection between the film layers.

(I) Embodiment

Example 1

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is PTN28)/12.48nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/1.0nm, silicon dioxide layer 3-4/34.5nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.5nm, silicon aluminum composite oxide layer 3-101.66/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.6nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/71.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm);

The method for preparing the resin lens comprises the following steps:

S1: Making a hard layer: immerse the resin lens substrate cleaned by ultrasonic wave into a hardening liquid aqueous solution of 27% by weight and model Z117 at a dipping temperature of 15°C, and pull out the solution at a speed of 2.0 mm/s after dipping for 5 seconds; after drying at 80°C for 3 hours, take out the substrate and send it to a drying oven for drying and curing at a curing temperature of 120°C and a curing time of 150 minutes, thereby obtaining a resin lens with a hard layer;

S2: preparing a clear background color infrared-proof film layer: in a vacuum coating machine, using a vacuum coating process, evaporating the solid film layer material and then transmitting it through the gas phase, and depositing it into a thin film on the surface of the resin lens obtained in step S1 to form a clear background color infrared-proof film layer, specifically comprising the following steps:

S21: forming a silicon-aluminum composite oxide layer on the surface of the resin lens obtained in step S1. Under the conditions of a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 50-70°C, and an ion source-assisted process, a high-energy electron beam is used to heat the silicon-aluminum composite oxide at a rate of Depositing the evaporated silicon-aluminum composite oxide in the form of nano-scale molecules to obtain a resin lens containing a first silicon-aluminum composite oxide layer;

S22: Forming a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S21. On the surface of the resin lens obtained in step S21, under the conditions of background vacuum ≤ 3×10 ^-3 Pa, temperature in the coating chamber of 50-70°C, and ion source assisted process, a high-energy electron beam is used to heat the titanium-niobium composite oxide at a rate of depositing the evaporated titanium-niobium composite oxide in the form of nano-scale molecules to obtain a resin lens containing a second titanium-niobium composite oxide layer;

S23: forming a titanium nitride layer on the surface of the resin lens obtained in step S22, specifically comprising the following steps: S231: first evacuating to a background vacuum of ≤8×10 ^-4 Pa, and then bombarding with an ion source Hall source for 60 seconds, the ion source bombardment parameters are: anode voltage: 110V, anode current: 3A, auxiliary gas is Ar, flow rate is 10sccm; S232: depositing under the ion source assisted process, using a high-energy electron beam to heat TiN at a rate The evaporated TiN is deposited in the form of nano-scale molecules, and the auxiliary parameters of the ion source are: anode voltage: 110V, anode current: 3A, auxiliary gases are Ar and _N2 , Ar flow rate is 10sccm, _N2 flow rate is: 5sccm; S233: continue to bombard the TiN film layer surface with the ion source Hall source for 30 seconds, and the bombardment parameters are: anode voltage: 110V, anode current: 3A, auxiliary gases are Ar and _N2 , Ar flow rate is 10sccm, _N2 flow rate is: 5sccm.

S24: The surface of the resin lens obtained in S23 is heated by a high-energy electron beam at a rate of 10000 t/ _cm2 , with a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 50-70°C, and an ion source assisted process. The evaporated SiO ₂ is deposited in the form of nano-scale molecules to obtain a resin lens containing a SiO ₂ layer; the auxiliary parameters of the ion source are: anode voltage: 110V, anode current: 3A, auxiliary gas is Ar, and the flow rate is 10sccm.

S25: repeating step S22 to form a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S24;

S26: repeat step S21 to form a silicon-aluminum composite oxide layer on the surface of the resin lens obtained in step S25;

S27: Repeat step S22 to form a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S26;

S28: The surface of the resin lens obtained in S27 is heated by a high-energy electron beam at a rate of 1000 Å to 1000 Å under the conditions that the background vacuum is ≤3×10 ^-3 Pa, the temperature in the coating chamber is 50-70°C, and an ion source is used to assist the process. Depositing the evaporated ITO in the form of nano-scale molecules to obtain a resin lens containing an ITO layer;

S29: continuing to use the vacuum coating process on the surface of the resin lens obtained in S28, repeating the process steps of S21, and then forming a layer of resin lens containing a silicon-aluminum composite oxide layer;

S3: preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in step S29: continuing to use a vacuum coating process on the surface of the lens obtained in step S29, using a high-energy electron beam to heat the material at a rate of 1000 ℃ under the conditions that the background vacuum degree is ≤3×10 ^-3 Pa and the temperature in the coating chamber is 60°C. The evaporated waterproof material containing C ₁₂ F ₂₇ N is deposited in the form of nano-scale molecules on the surface of the resin lens obtained in S24 to obtain the lens.

Example 2

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (SK1.56-UV405); a hardening layer 2 (VH56)/1-2.6 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. for development and production, the material model is PTN28)/11.8nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/1.0nm, silicon dioxide layer 3-4/35.26nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.2nm, silicon aluminum composite oxide layer 3-6/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.7nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/70.83nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm).

The method for preparing the resin lens comprises the following steps:

S1: Making a hard layer: immerse the resin lens substrate cleaned by ultrasonic wave into a 30% by weight hardening liquid aqueous solution of model VH56 at a dipping temperature of 15°C, and pull out the solution at a speed of 2.0 mm/s after dipping for 5 seconds; after drying at 80°C for 3 hours, take out the substrate and send it to a drying oven for drying and curing at a curing temperature of 120°C and a curing time of 150 minutes, thereby obtaining a resin lens with a hardening layer;

The remaining steps are the same as in Example 1.

Example 3

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-7-UV405); a hardening layer 2 (Z118)/1-2.6 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. for development and production, the material model is PTN28)/14.34nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/1.0nm, silicon dioxide layer 3-4/34.1nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/116.05nm, silicon aluminum composite oxide layer 3-6/160.78nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.34nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/70.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm).

The method for preparing the resin lens comprises the following steps:

S1: Making a hard layer: immerse the resin lens substrate cleaned by ultrasonic wave into a 27% by weight hardening liquid aqueous solution of model Z118 at a temperature of 15°C, and pull out the solution at a speed of 2.0 mm/s after immersion for 5 seconds; after drying at 80°C for 3 hours, take out the substrate and send it to a drying oven for drying and curing at a temperature of 120°C for 150 minutes, thereby obtaining a resin lens with a hard layer;

The remaining steps are the same as in Example 1.

Example 4

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. for development and production, the material model is PTN28)/12.48nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/0.75nm, silicon dioxide layer 3-4/34.5nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.5nm, silicon aluminum composite oxide layer 3-6/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.6nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/71.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm);

The preparation method is the same as that of Example 1.

(II) Comparative Example

Comparative Example 1

A clear bottom color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardened layer 2 (Z117)/2.6-3 μm; a light green infrared-proof film layer 3 comprising: a _SiO2 layer 3-1/24.6 nm, a _ZrO2 layer 3-2/8.42 nm, a SiO2 layer 3-3/51.42 nm, a _ZrO2 layer 3-4/118.72 nm, a _SiO2 layer 3-5/160.59 nm, a _ZrO2 layer 3-6/80.64 nm _, an ITO layer 3-7/5 nm; a _SiO2 layer 3-8/66.3 nm; a waterproof layer 4 (adopting a waterproof material containing _C12F27N / ₁₀ nm);

The preparation method comprises the following steps:

S1: Making a hard layer: immerse the resin lens substrate cleaned by ultrasonic wave into a 27% by weight hardening liquid aqueous solution of model Z117 at a dipping temperature of 15°C, and pull out the solution at a speed of 2.0 mm/s after dipping for 5 seconds; after drying at 80°C for 3 hours, take out the substrate and send it to a drying oven for drying and curing at a curing temperature of 120°C for 150 minutes, thereby obtaining a resin lens with a hardening layer;

S2: preparing a clear background color infrared-proof film layer: in a vacuum coating machine, using a vacuum coating process, evaporating the solid film layer material and then transmitting it through the gas phase, and depositing it into a thin film on the surface of the resin lens obtained in step S1 to form a clear background color infrared-proof film layer, specifically comprising the following steps:

S21: comprising the following steps:

S211: The surface of the resin lens obtained in S1 is heated by high-energy electron beam at a rate of 10000 t/ _cm2 , with a background vacuum of ≤3×10 ^-3 Pa, a temperature of 60°C in the coating chamber, and no ion source auxiliary process. The evaporated SiO ₂ is deposited in the form of nano-scale molecules to obtain a resin lens containing a first SiO ₂ layer;

S212: The surface of the resin lens obtained in S211 is heated by high-energy electron beam at a rate of ₁₀₀₀ Å to 2000 Å under the conditions of background vacuum ≤ 3×10 ^-3 Pa, temperature in the coating chamber of 60°C, and no ion source auxiliary process. The evaporated ZrO ₂ is deposited in the form of nano-scale molecules to obtain a resin lens containing a second ZrO ₂ layer;

S213: repeating steps S211 and S212 to alternately form a third SiO ₂ layer, a fourth ZrO ₂ layer, a fifth SiO ₂ layer, and a sixth ZrO ₂ layer, respectively, to form a resin lens including a third SiO ₂ layer, a fourth ZrO ₂ layer, a fifth SiO ₂ layer, and a sixth ZrO ₂ layer;

S22: On the surface of the resin lens obtained in S21, under the conditions of background vacuum ≤3×10 ^-3 Pa, temperature in the coating chamber of 60°C, and ion source assisted process, high energy electron beam is used to heat ITO at a rate of Depositing the evaporated ITO in the form of nano-scale molecules to obtain a resin lens containing a seventh ITO layer;

S23: continuing to use the vacuum coating process on the surface of the resin lens obtained in S22, repeating the process steps of S211, and then forming a resin lens containing an eighth _SiO2 layer;

S3: preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in S23: continuing to use the vacuum coating process on the surface of the lens obtained in step S2, using a high-energy electron beam to heat the material at a rate of 1000 ℃ under the conditions that the background vacuum degree is ≤3×10 ^-3 Pa and the temperature in the coating chamber is 60°C. The evaporated waterproof material containing C ₁₂ F ₂₇ N is deposited in the form of nano-scale molecules on the surface of the resin lens obtained in S24 to obtain the lens.

Comparative Example 2

A blue anti-reflection and infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8- _UV405 ); a hardening layer 2 (Z117)/2.6-3μm; an anti-reflection layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of _SiO2 and _Al2O3 is: 92% _SiO2 : 8% _Al2O3 ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., _Ltd. to develop and produce, the material model is SA56)/27.6nm, a titanium- _{niobium composite oxide layer 3-2 (wherein the molar percentage of TiO2 and Nb2O5 is : 80} % _TiO2 : 20% _Nb2O5 ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. for development and production, the material model is PTN28)/15.45nm, silicon-aluminum composite oxide layer 3-3/31.42nm (material is the same as 3-1), titanium-niobium composite oxide layer 3-4 (material is the same as 3-2)/98.9nm, silicon-aluminum composite oxide layer 3-5/171.92nm (material is the same as 3-1), titanium _- niobium composite oxide layer 3-6 (material is the same as 3-2)/91.96nm, ITO layer 3-7/5nm; silicon-aluminum composite oxide layer 3-8/75.8nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing _C12F27N /10nm);

The method for preparing the resin lens comprises the following steps:

S1: Making a hard layer: immerse the resin lens substrate cleaned by ultrasonic wave into a 27% by weight hardening liquid aqueous solution of model Z117 at a dipping temperature of 15°C, and pull out the solution at a speed of 2.0 mm/s after dipping for 5 seconds; after drying at 80°C for 3 hours, take out the substrate and send it to a drying oven for drying and curing at a curing temperature of 120°C for 150 minutes, thereby obtaining a resin lens with a hardening layer;

S2: Preparation of anti-reflection and infrared protection layer: In a vacuum coating machine, a vacuum coating process is adopted to evaporate the solid film material and then transmit it through the gas phase, and then deposit it into a thin film on the surface of the resin lens obtained in step S1 to form an anti-reflection and infrared protection layer, which specifically includes the following steps:

S21: comprising the following steps:

S211: On the surface of the resin lens obtained in S1, under the conditions of background vacuum ≤3×10 ^-3 Pa, temperature in the coating chamber of 60°C, and ion source assisted process, high energy electron beam is used to heat the silicon aluminum composite oxide at a rate of Depositing the evaporated silicon-aluminum composite oxide in the form of nano-scale molecules to obtain a resin lens containing a first silicon-aluminum composite oxide layer;

S212: The surface of the resin lens obtained in S211 is heated by a high-energy electron beam at a rate of 1000 Å under the conditions of a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 60°C, and an ion source-assisted process. depositing the evaporated titanium-niobium composite oxide in the form of nano-scale molecules to obtain a resin lens containing a second titanium-niobium composite oxide layer;

S213: repeating steps S211 and S212 to alternately form a third silicon-aluminum composite oxide layer, a fourth titanium-niobium composite oxide layer, a fifth silicon-aluminum composite oxide layer, and a sixth titanium-niobium composite oxide layer, respectively, that is, forming a resin lens including a third silicon-aluminum composite oxide layer, a fourth titanium-niobium composite oxide layer, a fifth silicon-aluminum composite oxide layer, and a sixth titanium-niobium composite oxide layer;

S22: On the surface of the resin lens obtained in S21, under the conditions of background vacuum ≤3×10 ^-3 Pa, temperature in the coating chamber of 60°C, and ion source assisted process, high energy electron beam is used to heat ITO at a rate of Depositing the evaporated ITO in the form of nano-scale molecules to obtain a resin lens containing a seventh ITO layer;

S23: continuing to use the vacuum coating process on the surface of the resin lens obtained in S22, repeating the process steps of S211, and then forming a resin lens containing an eighth silicon-aluminum composite oxide layer;

S3: preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in S23: continuing to use the vacuum coating process on the surface of the lens obtained in step S2, using a high-energy electron beam to heat the material at a rate of 1000 ℃ under the conditions that the background vacuum degree is ≤3×10 ^-3 Pa and the temperature in the coating chamber is 60°C. The evaporated waterproof material containing C ₁₂ F ₂₇ N is deposited in the form of nano-scale molecules on the surface of the resin lens obtained in S24 to obtain the lens.

Comparative Example 3

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; an anti-reflection layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. for development and production, the material model is PTN28)/13.48nm, silicon-aluminum composite oxide layer 3-3/34.5nm (material is the same as 3-1), titanium-niobium composite oxide layer 3-4 (material is the same as 3-2)/114.5nm, silicon-aluminum composite oxide layer 3-5/160.4nm (material is the same as 3-1), titanium _- niobium composite oxide layer 3-6 (material is the same as 3-2)/101.62nm, ITO layer 3-7/5nm; silicon-aluminum composite oxide layer 3-8/73nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing _C12F27N /10nm);

Its preparation process and method are the same as those of Comparative Example 2.

Comparative Example 4

A clear bottom color infrared-proof resin lens comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; an anti-reflection layer 3 comprising: a _SiO2 layer 3-1/26.6 nm, a _TiO2 layer 3-2/13.35 nm, a _SiO2 layer 3-3/34.8 nm, a _TiO2 layer 3-4/113.81 nm, a _SiO2 layer 3-5/161.65 nm, a _TiO2 layer 3-6/101.11 nm, an ITO layer 3-7/5 nm; a _SiO2 layer 3-8/73.6 nm; a waterproof layer 4 (using a waterproof material containing _C12F27N /10 _nm ); a preparation method thereof comprises the following steps:

S1: Making a hard layer: immerse the resin lens substrate cleaned by ultrasonic wave into a 27% by weight hardening liquid aqueous solution of model Z117 at a dipping temperature of 15°C, and pull out the solution at a speed of 2.0 mm/s after dipping for 5 seconds; after drying at 80°C for 3 hours, take out the substrate and send it to a drying oven for drying and curing at a curing temperature of 120°C for 150 minutes, thereby obtaining a resin lens with a hardening layer;

S2: preparing a clear background color infrared-proof film layer: in a vacuum coating machine, using a vacuum coating process, evaporating the solid film layer material and then transmitting it through the gas phase, and depositing it into a thin film on the surface of the resin lens obtained in step S1 to form a clear background color infrared-proof film layer, specifically comprising the following steps:

S21: comprising the following steps:

S211: The surface of the resin lens obtained in S1 is heated by high-energy electron beam at a rate of 10000 t/ _cm2 , with a background vacuum of ≤3×10 ^-3 Pa, a temperature of 60°C in the coating chamber, and an ion source assisted process. The evaporated SiO ₂ is deposited in the form of nano-scale molecules to obtain a resin lens containing a first SiO ₂ layer;

S212: The surface of the resin lens obtained in S211 is heated by a high-energy electron beam at a rate of 10000 t/ _cm2 , with a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 60°C, and an ion source assisted process. Depositing the evaporated TiO ₂ in the form of nano-scale molecules to obtain a resin lens containing a second TiO ₂ layer;

S213: repeating steps S211 and S212 to alternately form a third SiO ₂ layer, a fourth TiO ₂ layer, a fifth SiO ₂ layer, and a sixth TiO ₂ layer, respectively, to form a resin lens including a third SiO ₂ layer, a fourth TiO ₂ layer, a fifth SiO ₂ layer, and a sixth TiO ₂ layer;

S22: On the surface of the resin lens obtained in S21, under the conditions of background vacuum ≤3×10 ^-3 Pa, temperature in the coating chamber of 60°C, and ion source assisted process, high energy electron beam is used to heat ITO at a rate of Depositing the evaporated ITO in the form of nano-scale molecules to obtain a resin lens containing a seventh ITO layer;

S23: continuing to use the vacuum coating process on the surface of the resin lens obtained in S22, repeating the process steps of S211, and then forming a resin lens containing an eighth _SiO2 layer;

S3: preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in S23: continuing to use the vacuum coating process on the surface of the lens obtained in step S2, using a high-energy electron beam to heat the material at a rate of 1000 ℃ under the conditions that the background vacuum degree is ≤3×10 ^-3 Pa and the temperature in the coating chamber is 60°C. The evaporated waterproof material containing C ₁₂ F ₂₇ N is deposited in the form of nano-scale molecules on the surface of the resin lens obtained in S24 to obtain the lens.

Comparative Example 5

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is PTN28)/12.48nm, SiO-Cr absorption layer 3-3 (SiO:Cr molar ratio is 1:1, sintered by Danyang Keda Coating Materials Co., Ltd.)/1.2nm, silicon dioxide layer 3-4/34.5nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.5nm, silicon aluminum composite oxide layer 3-6/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.6nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/71.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm);

The preparation method thereof is the same as that of Example 1 except for the 3-3 SiO-Cr absorption layer.

The preparation process of the SiO-Cr absorption layer is as follows: a SiO-Cr layer is formed on the surface of the resin lens obtained in step S22. First, the vacuum is evacuated to a background vacuum degree of ≤1.2×10 ^-4 Pa. Then, the SiO-Cr is deposited under the ion source Hall source assisted process, and a high-energy electron beam is used to heat the SiO-Cr at a rate of The evaporated SiO-Cr is deposited in the form of nano-scale molecules to obtain a resin lens containing a SiO-Cr layer. The auxiliary parameters of the ion source here are: anode voltage: 110V, anode current: 3A, and Ar flow rate of 12sccm.

Comparative Example 6

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is PTN28)/12.48nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/1.0nm, silicon dioxide layer 3-4/34.5nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.5nm, silicon aluminum composite oxide layer 3-6/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.6nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/71.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm);

The preparation method thereof is the same as that of Example 1 except for the 3-3 layers of titanium nitride.

The preparation process of titanium nitride is as follows: a titanium nitride layer is formed on the surface of the resin lens obtained in step S22. First, evacuate to a background vacuum of ≤8×10 ^-4 Pa. Then bombard with an ion source Hall source for 60 seconds. The ion source bombardment parameters are: anode voltage: 110V, anode current: 3A, auxiliary gas is Ar, and the flow rate is 10sccm. Then, deposit under the ion source Hall source assisted process, use a high-energy electron beam to heat TiN at a rate The evaporated TiN is deposited in the form of nano-scale molecules to obtain a resin lens containing a TiN layer. The ion source auxiliary parameters here are: anode voltage: 110V, anode current: 3A, Ar flow rate is 12sccm, and there is no nitrogen flow rate. After obtaining a resin lens containing a TiN layer, the TiN surface is bombarded with an ion source for 30 seconds, and its ion source parameters are the same as the ion source auxiliary parameters of this layer.

Comparative Example 7

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is PTN28)/12.48nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/1.0nm, silicon dioxide layer 3-4/34.5nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.5nm, silicon aluminum composite oxide layer 3-6/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.6nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/71.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm);

The preparation method is the same as that of Example 1 except for the 3-3 layer of titanium nitride. The preparation process of titanium nitride is as follows: S23: Form a titanium nitride layer on the surface of the resin lens obtained in step S22. First, evacuate to a background vacuum of ≤8×10 ^-4 Pa. No ion source Hall source pre-bombardment. Directly deposit under the ion source Hall source assisted process, use a high energy electron beam to heat TiN at a rate The evaporated TiN is deposited in the form of nano-scale molecules to obtain a resin lens containing a TiN layer. The ion source auxiliary parameters here are: anode voltage: 110V, anode current: 3A, Ar flow rate is 10sccm, and nitrogen flow rate is: 5sccm. After obtaining a resin lens containing a TiN layer, continue to bombard the TiN surface with an ion source for 30 seconds. The ion source parameters are the same as the ion source auxiliary parameters of this layer.

Comparative Example 8

A clear base color infrared-proof resin lens, which comprises, in order: a resin lens substrate 1 (MR-8-UV405); a hardening layer 2 (Z117)/2.6-3 μm; a clear base color infrared-proof film layer 3 comprising: a silicon-aluminum composite oxide layer 3-1 (wherein the molar percentage of SiO ₂ and Al ₂ O ₃ is: 92% SiO ₂ : 8% Al ₂ O ₃ ; commissioned by Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is SA56)/26 nm, a titanium-niobium composite oxide layer 3-2 (wherein the molar percentage of TiO ₂ and Nb ₂ O ₅ is: 80% TiO ₂ : 20% Nb ₂ O ₅ ; Entrusted to Changzhou Zhanchi Optoelectronics Technology Co., Ltd. to develop and produce, the material model is PTN28)/12.48nm, titanium nitride layer 3-3 (molecular formula TiN, purity above 99.9%, sintered by Changzhou Zhanchi Optoelectronics Technology Co., Ltd.)/1.0nm, silicon dioxide layer 3-4/34.5nm (molecular formula SiO ₂ , purity 99.99%, sintered by Danyang Keda Coating Materials Co., Ltd.), titanium niobium composite oxide layer 3-5 (material is the same as 3-2)/114.5nm, silicon aluminum composite oxide layer 3-6/160.4nm (material is the same as 3-1); titanium niobium composite oxide layer 3-7 (material is the same as 3-2)/101.6nm; ITO layer 3-8/5nm; silicon aluminum composite oxide layer 3-9/71.0nm (material is the same as 3-1); waterproof layer 4 (using waterproof material containing C ₁₂ F ₂₇ N/10nm);

The preparation method thereof is the same as that of Example 1 except for the 3-3 layers of titanium nitride.

The preparation process of titanium nitride is S23: forming a titanium nitride layer on the surface of the resin lens obtained in step S22. First, evacuate to a background vacuum of ≤3×10 ^-3 Pa (the vacuum is not specifically controlled). Then bombard with an ion source Hall source for 60 seconds. The ion source bombardment parameters are: anode voltage: 110V, anode current: 3A, auxiliary gas is Ar, and the flow rate is 10sccm. Then, deposit under the ion source Hall source assisted process, use a high-energy electron beam to heat TiN at a rate of The evaporated TiN is deposited in the form of nano-scale molecules to obtain a resin lens containing a TiN layer. Here, the ion source auxiliary parameters are: anode voltage: 110V, anode current: 3A, Ar flow rate: 10sccm, nitrogen flow rate: 5sccm. After obtaining a resin lens containing a TiN layer, the TiN surface is bombarded with an ion source for 30 seconds, and its ion source parameters are the same as the ion source auxiliary parameters of this layer.

2. Experimental Examples

The list of materials for the main embodiments and comparative examples is as follows: the one containing TiN or SiO-Cr is a 9-layer anti-infrared film structure, and the one not containing TiN or SiO-Cr is an 8-layer anti-infrared film system.

Table 1. Comparison of materials in Examples and Comparative Examples

1. Determine the average reflectivity, transmittance, yellow index and infrared protection effect of the lens

1.1 Determination of the average reflectivity, transmittance and infrared protection effect of Examples 1 to 4 and Comparative Examples 1 to 8

For the lenses prepared in Examples 1 to 4 and Comparative Examples 1 to 8, the average reflectivity (average reflectivity: refers to the visual average reflectivity under C light (a light source with a color temperature of 6774K defined in CIE) illumination, here refers to the reflectivity of a single side), the average transmittance (average transmittance: refers to the visual average transmittance under C light (a light source with a color temperature of 6774K defined in CIE) illumination, here refers to the transmittance of the same film system coated on both sides), the yellow index (refers to the yellow index of the lens calculated with reference to QB-T-2506-2001 after coating on both sides) and the near-infrared transmittance (near-infrared average transmittance: here refers to the near-infrared cutoff rate of the lens calculated with reference to QB-T-2506-2017 after coating on both sides) were measured, and the measurement results are recorded in Table 2 below:

Table 2. Comparison of reflectivity, infrared rejection and yellowness index

From Comparative Examples 2 and 3, it can be seen that the infrared blocking rate of the green film is higher and the yellow index is lower. The TiN layer with a special process is used, and the infrared blocking rate is further improved and the yellow index is further reduced. The visual effect of the lens is clearer.

1.2 Determining the blue light protection effect of lenses

Refer to the national standard GB/T38120-2019 to check whether the lenses meet the standards.

Table 3. Comparison of blue light protection index and yellow index

1.3 Comparison of the impact of TiN process on anti-blue light standards and yellow index

Test the transmission and reflection of a single surface and calculate the absorption results as follows:

Table 4. Effect of TiN process on anti-blue light index and yellow index

The general process uses SiO-Cr as the absorption layer, which can effectively meet the needs of blue light protection. However, its yellow-green light absorption is low, which will lead to an increase in the yellow index. Most weak absorption materials have this characteristic.

Strictly controlling the preparation process of the TiN film layer helps to achieve the expected technical effect of the film layer. (1) When the vacuum control of TiN is not strict, there will be a tendency to oxidize, thereby reducing the absorption of the film layer, and the absorption of yellow-green light and infrared light will decrease faster, resulting in an increase in the yellow index, and the lens will be visually yellow and unclear; (2) When TiN is not assisted by an ion source, the film layer is loose and the nitrogen content will be reduced during the evaporation process. When other layers are plated, oxidation will be supplemented. As a result, there will be a tendency to oxidize, thereby reducing the absorption of the film layer, and the absorption of yellow-green light and infrared light will decrease faster, resulting in an increase in the yellow index, and the lens will be visually yellow and unclear; (3) When the TiN ion source is assisted without nitrogen assistance, the film layer will be metallized (insufficient nitridation) and the absorption will increase sharply. The absorption of blue light increases much faster than that of yellow-green light and infrared, resulting in an increase in the yellow index, and the lens will be visually yellow and gray and unclear. The use of the specific process of the present invention to prepare the TiN layer can effectively increase the blocking absorption of near-infrared, control the absorption of blue light, and increase the absorption of yellow light, thereby reducing the yellow index and making the lens clearer and more beautiful.

2. High temperature resistance, durability and high temperature adhesion test

2.1 Temperature resistance test:

After the samples (Examples 1 to 4 and Comparative Examples 1 to 8) were completed, the heat resistance of the samples was tested after being stored for one week. The test method for heat resistance is based on Article 5.8 of the National Heat Resistance Standard for Resin Lenses (GB10810.4-2012): Pass the 55°C 30-minute baking test. After passing the test, the same method is used to increase the temperature by 5°C for 30 minutes each time until the lens shows failure phenomena such as film cracks or orange peel, and the highest qualified temperature is recorded. The results are recorded in Table 5 below.

2.2 High temperature adhesion test:

Adhesion test refers to the film adhesion test in accordance with Article 5.9 of the national standard GB10810.4-2012. High-temperature film adhesion test refers to Wanxin Company referring to Article 5.9 of the national standard GB10810.4-2012, changing the boiling conditions to 90±2℃ for 60 minutes, and other test methods are the same. Adhesion and high-temperature adhesion test results: Grade A refers to no film removal or the film removal area is less than 5%, Grade B refers to the film removal area between 5% and 15%, and Grade C (unqualified) refers to the film removal area significantly greater than 15%. In order to verify the product adhesion distribution, high-temperature adhesion tests were performed from 5 different positions in the coating room. The test results of Examples 1 to 4 and Comparative Examples 1 to 8 are recorded in Table 5 below.

2.3 High temperature and high humidity test

The photovoltaic industry and the optical communication industry use high temperature and high humidity to evaluate the durability of products. Referring to the test standards of the photovoltaic industry (GB/T 18911-2002, IEC61646:1996, Article 10.13) and the test methods of the optical communication industry (Ballcore Test, GR-1221-Core, Article 6.2.5), the high temperature and high humidity test and debugging of the resin lens is defined as: storage at 85°C and 85% humidity for 12 hours, and checking whether the prepared lens has obvious failure phenomena such as film cracks or orange peel; 3 resin lenses are placed in different positions for each high temperature and high humidity test. The test results of Examples 1 to 4 and Comparative Examples 1 to 8 are recorded in Table 5 below.

Table 5 High temperature resistance, durability and high temperature adhesion test results

It can be seen that, under the condition that other conditions remain unchanged, the high-refractive index material of the lens made of titanium-niobium composite oxide has better high-temperature resistance, high-temperature adhesion and durability than other conventional materials; the low-refractive index material made of silicon-aluminum composite oxide has better high-temperature resistance, high-temperature adhesion and durability than other conventional materials; we use these two specific ratios of materials to prepare the film system and its appropriate process to ensure the high temperature resistance and durability of the clear base color anti-infrared products.

Claims (17)

A clear-base-color, blue-light-proof, infrared-proof, and high-temperature-resistant resin lens, characterized in that it comprises: a resin lens substrate, a hardened layer, and a clear-base-color infrared-proof layer; wherein the resin lens substrate, the hardened layer, and the clear-base-color infrared-proof film layer are arranged in sequence, the hardened layer is located on the surface of the resin lens substrate, and the clear-base-color infrared-proof film layer is located on the surface of the hardened layer. The clear base color, blue light proof, infrared proof, and high temperature resistant resin lens according to claim 1 is characterized in that the clear base color, infrared proof, and high temperature resistant resin lens also includes a waterproof layer, and the waterproof layer is located on the surface of the clear base color, infrared proof, and high temperature resistant film layer. The clear base color, blue light proof, infrared proof and high temperature resistant resin lens according to claim 1 is characterized in that the material of the hardened layer is silicone; further preferably, the silicone contains at least Ti element. The clear background color, blue light protection, infrared protection and high temperature resistant resin lens according to claim 1 is characterized in that the clear background color infrared protection film layer includes a silicon-aluminum composite oxide layer, a titanium-niobium composite oxide layer, a tin-doped indium oxide (i.e., ITO) layer and a titanium nitride (TiN) layer; further, the clear background color infrared protection film layer includes three layers of silicon-aluminum composite oxide layers, three layers of titanium-niobium composite oxide layers, a layer of tin-doped indium oxide (i.e., ITO) layer, a layer of silicon dioxide layer and a layer of titanium nitride (TiN). The clear-bottom-color _, blue-light-proof, infrared-proof, and high-temperature-resistant resin lens according to claim 4 is characterized in that the silicon-aluminum composite oxide layer is composed of a composite material of _SiO2 and _Al2O3 , and the molar fraction of _SiO2 in the composite material is 70% to 95%; further preferably, _SiO2 accounts for 92% of the molar fraction of the composite material. The clear-bottom-color, blue-light-proof, infrared-proof, and high-temperature-resistant resin lens according to claim 4 is characterized in that the titanium- _niobium composite oxide layer is composed of a composite material of _TiO2 and _Nb2O5 , wherein _TiO2 accounts for 10% to 90% of the molar fraction of the composite material; preferably, _TiO2 accounts for 80% of the molar fraction of the composite material. The clear base color, blue light proof, infrared proof and high temperature resistant resin lens according to claim 4 is characterized in that the purity of TiN in the titanium nitride layer is greater than 99.9wt%. According to claim 1, the clear base color blue light proof infrared proof high temperature resistant resin lens, The invention is characterized in that the thickness of the hardened layer is 1 to 5 μm. The clear base color, blue light protection, infrared protection, and high temperature resistance resin lens according to claim 1 is characterized in that the thickness of the clear base color infrared protection film layer is 290 to 950 nm. The clear base color, blue light proof, infrared proof and high temperature resistant resin lens according to claim 2 is characterized in that the thickness of the waterproof layer is 4 to 20 nm. According to any one of claims 1 to 10, the clear base color blue light proof infrared proof high temperature resistant resin lens is characterized in that the average reflectivity of the clear base color blue light proof infrared proof resin high temperature resistant lens is ≤1.5%. According to any one of claims 1 to 10, the clear-base-color, blue-light-proof, infrared-proof, and high-temperature-resistant resin lens has a near-infrared blocking rate of >55%. According to any one of claims 1 to 10, the clear base color blue light proof infrared proof high temperature resistant resin lens has a yellow index of ≤4.5%. A method for preparing the clear base color blue light and infrared resistant resin high temperature resistant lens according to any one of claims 1 to 10, characterized in that it comprises the following steps: S1: preparing a hard layer: forming a hard layer on the surface of a resin lens substrate, that is, obtaining a resin lens containing a hard layer; S2 preparing a clear background color infrared-proof film layer: forming the clear background color infrared-proof film layer on the surface of the resin lens obtained in S1, that is, obtaining a resin lens containing a clear background color infrared-proof film layer, specifically comprising: S21: forming a resin lens having a first silicon-aluminum composite oxide layer and a second titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S1; S22: forming a third layer of a resin lens containing a titanium nitride layer on the surface of the resin lens obtained in step S21; S23: forming a fourth _SiO2- containing resin lens on the surface of the resin lens obtained in step S22; S24: forming a fifth titanium-niobium composite oxide layer, a sixth silicon-aluminum composite oxide layer, and a seventh titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S23. S25: forming an eighth ITO-containing resin lens on the surface of the resin lens obtained in step S24; S26: forming a ninth layer of a resin lens containing a silicon-aluminum composite oxide layer on the surface of the resin lens obtained in step S25; S3: preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in step S2. According to the preparation method of the clear base color anti-blue light and anti-infrared resin high temperature resistant lens as described in claim 14, it is characterized in that the step of preparing the hard layer in S1 comprises: immersing the resin lens substrate cleaned by ultrasonic wave into a hardening liquid aqueous solution with a mass percentage of 25-30%, the immersion temperature is 10-20°C, and after immersion for 4-8 seconds, the solution is pulled out at a speed of 1.0-3.0 mm/s, and then it is dried at 70-90°C for 2-5 hours, and then the substrate is taken out and sent to a drying oven for drying and curing, the curing temperature is 100-150°C, and the curing time is 120-180min, so as to obtain a resin lens containing a hardened layer. According to the method for preparing the clear background color anti-blue light and anti-infrared resin high temperature resistant lens according to claim 14, it is characterized in that the process of preparing the clear background color anti-infrared film layer in step S2 comprises: in a vacuum coating machine, using a vacuum coating process, evaporating the silicon aluminum composite oxide layer, titanium niobium composite oxide, titanium nitride, silicon dioxide and ITO solid film layer materials, and then transmitting them through the gas phase, and depositing them into a thin film on the surface of the resin lens obtained in step S1 to form a clear background color anti-infrared film layer, specifically comprising the following steps: S21: forming a first layer of silicon-aluminum composite oxide on the surface of the resin lens obtained in step S1, heating the silicon-aluminum composite oxide with a high-energy electron beam at a rate of 1000 Å under the conditions of a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 50-70°C, and an ion source-assisted process. Depositing the evaporated silicon-aluminum composite oxide in the form of nano-scale molecules to obtain a resin lens containing a first silicon-aluminum composite oxide layer; S22: forming ^a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S21, heating the titanium-niobium composite oxide on the surface of the resin lens obtained in step S21 by using a high-energy electron beam at a rate of depositing the evaporated titanium-niobium composite oxide in the form of nano-scale molecules to obtain a resin lens containing a second titanium-niobium composite oxide layer; S23: forming a titanium nitride layer on the surface of the resin lens obtained in step S22, specifically comprising: S231: first evacuate to a background vacuum of ≤8×10 ^-4 Pa, then bombard with an ion source Hall source for 50 to 80 seconds. The ion source bombardment parameters are: anode voltage: 90 to 140 V, anode current: 2.5 to 5 A, auxiliary gas is Ar, and the flow rate is 5 to 20 sccm; S232: Deposition in an ion source assisted process, using a high energy electron beam to heat TiN at a rate The evaporated TiN is deposited in the form of nano-scale molecules, and the auxiliary parameters of the ion source are: anode voltage: 90-140V, anode current: 2.5-5A, auxiliary gas is Ar and _N2 , Ar flow rate is 5-15sccm, _N2 flow rate is: 3-15sccm; S233: continue bombarding the TiN film surface with the ion source Hall source for 20 to 40 seconds, the bombardment parameters are: anode voltage: 90 to 140 V, anode current: 2.5 to 5 A, auxiliary gas is Ar and N ₂ , Ar flow rate is 5 to 15 sccm, N ₂ flow rate is: 3 to 15 sccm; S24: The surface of the resin lens obtained in S23 is heated by a high-energy electron beam at a rate of 10000 t/ _cm2 , with a background vacuum of ≤3×10 ^-3 Pa, a temperature in the coating chamber of 50-70°C, and an ion source assisted process. The evaporated SiO ₂ is deposited in the form of nano-scale molecules to obtain a resin lens containing a SiO ₂ layer; S25: repeating step S22 to form a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S24; S26: repeat step S21 to form a silicon-aluminum composite oxide layer on the surface of the resin lens obtained in step S25; S27: repeat step S22 to form a titanium-niobium composite oxide layer on the surface of the resin lens obtained in step S26; S28: The surface of the resin lens obtained in S27 is heated by a high-energy electron beam at a rate of 1000 Å to 1000 Å under the conditions that the background vacuum is ≤3×10 ^-3 Pa, the temperature in the coating chamber is 50-70°C, and an ion source is used to assist the process. Depositing the evaporated ITO in the form of nano-scale molecules to obtain a resin lens containing an ITO layer; S29: On the surface of the resin lens obtained in S28, continue to use the vacuum coating process, repeat the process steps of S21, and then form a layer of resin lens containing a silicon-aluminum composite oxide layer. According to the method for preparing the clear background color blue light and infrared resistant resin high temperature resistant lens of claim 14, it is characterized in that in the step S3, forming a waterproof layer on the surface of the resin lens obtained in step S2 comprises the following steps: continuing to use the vacuum coating process on the surface of the lens obtained in step S29, under the conditions that the background vacuum degree is ≤3× ^10-3 Pa and the temperature in the coating chamber is 50-70°C, using a high energy electron beam to heat the material at a rate of The evaporated fluorine-containing waterproof material is deposited in the form of nano-scale molecules to obtain a resin lens containing a waterproof layer.