阅读说明：本技术 一种低应力耐高温树脂镜片及其制备方法 (Low-stress high-temperature-resistant resin lens and preparation method thereof ) 是由 黄昱勇 汤峰 张国军 于 2020-06-23 设计创作，主要内容包括：本发明提供了一种低应力耐高温树脂镜片及其制备方法,所述树脂镜片包括：依次排列的树脂镜片基片、加硬层、减反射层以及防水层；其中,所述加硬层位于所述树脂镜片基片表面,所述减反射层位于所述加硬层表面,所述防水层位于所述减反射层表面；所述镜片表面还设置有网格状分布的极细沟槽,所述沟槽延伸至所述镜片边沿,且所述沟槽深度大于等于防水层和减反射层厚度之和。本发明以低应力硅镁复合氧化物作为减反射层材料,通过调整制备工艺获得到了满足减反射率以及耐高温、耐久性能佳的树脂镜片,满足性能的同时能够达到量产,具有良好的应用及市场前景。(The invention provides a low-stress high-temperature-resistant resin lens and a preparation method thereof, wherein the resin lens comprises: the resin lens comprises a resin lens substrate, a hardening layer, an antireflection layer and a waterproof layer which are sequentially arranged; the hardening layer is positioned on the surface of the resin lens substrate, the antireflection layer is positioned on the surface of the hardening layer, and the waterproof layer is positioned on the surface of the antireflection layer; the surface of the lens is also provided with extremely fine grooves which are distributed in a latticed manner, the grooves extend to the edge of the lens, and the depth of each groove is greater than or equal to the sum of the thicknesses of the waterproof layer and the antireflection layer. According to the invention, the low-stress silicon-magnesium composite oxide is used as an antireflection layer material, the resin lens which meets the antireflection rate and has high temperature resistance and good durability is obtained by adjusting the preparation process, the performance is met, the mass production can be realized, and the resin lens has good application and market prospects.)

1. A low-stress high-temperature-resistant resin lens is characterized by comprising a resin lens substrate, a hardening layer and an antireflection layer which are sequentially arranged; the hardening layer is positioned on the surface of the resin lens substrate, and the antireflection layer is positioned on the surface of the hardening layer.

2. The resin lens according to claim 1, wherein the low stress and high temperature resistant resin lens further comprises a waterproof layer on the surface of the antireflection layer.

3. The resin lens according to claim 2, wherein the lens surface is further provided with a grid-like groove, and the groove extends to the lens edge; preferably, the grid-shaped grooves comprise 1-20 transverse grooves and 1-20 longitudinal grooves.

4. The resin lens according to claim 3, wherein the depth of the grid-shaped grooves is equal to or greater than the sum of the thicknesses of the waterproof layer and the antireflection layer; furthermore, the width of the latticed groove is 1-50 mu m.

5. The resin lens according to any one of claims 1 to 4, wherein the material of the hard coat layer is silicone; preferably, the organosilicon at least contains Ti element; furthermore, the thickness of the hardening layer is 1-5 μm.

6. The resin lens according to any one of claims 1 to 4, wherein the antireflection layer comprises a low stress silicon magnesium composite oxide layer, ZrO, or the like₂A layer and a tin-doped indium oxide layer; further preferably, the low-stress silicon-magnesium composite oxide is formed by SiO₂And MgO, in which SiO₂The content of the silicon-magnesium composite oxide accounts for 70 to 95 percent of the mole fraction of the low-stress silicon-magnesium composite oxide; further preferably, the thickness of the antireflection layer is 180-400 nm.

7. The resin lens according to any one of claims 1 to 4, wherein the material of the water-repellent layer is a fluorine-containing water-repellent material; furthermore, the thickness of the waterproof layer is 4-20 nm.

8. The resin lens according to any one of claims 1 to 4, wherein the average reflectance of the low-stress high-temperature resistant resin lens is less than or equal to 0.5%.

9. The method for preparing the low-stress high-temperature-resistant resin lens as claimed in any one of claims 1 to 8, which comprises the following steps:

s1 preparing a stiffening layer: forming a hardening layer on the surface of the resin lens substrate to obtain a resin lens containing the hardening layer;

s2 preparing an antireflection layer: forming the antireflection layer on the surface of the resin lens obtained in S1, that is, obtaining the resin lens containing the antireflection layer, specifically including:

s21: two low-stress silicon-magnesium composite oxide layers and two layers of ZrO are alternately and respectively formed on the surface of the resin lens obtained in step S1₂Layer, i.e. obtained comprising two low-stress silicon-magnesium composite oxide layers and two layers of ZrO₂A resin lens of the layer;

s22: forming a resin lens containing an ITO layer on the surface of the resin lens obtained in step S21;

s23: forming a resin lens containing a low-stress silicon-magnesium composite oxide layer on the surface of the resin lens obtained in step S22;

s3 preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in the step S23 to obtain a resin lens containing the waterproof layer;

s4 forming a trench: respectively forming transverse and longitudinal grooves on the surface of the resin lens obtained in the step S3 in a laser cutting mode, or shielding the surface of the resin lens obtained in the step S1 by using ultra-fine tough fibers, and then performing the steps S2 and S3 to form the grooves; preferably, the diameter of the tough ultrafine fibers is 1 to 30 μm; more preferably, the tough ultrafine fiber is a core of a single-mode optical fiber.

Technical Field

The invention relates to the technical field of resin lens preparation, in particular to a low-stress high-temperature-resistant resin lens and a preparation method thereof.

Background

In recent years, there is an increasing demand for optical resin lenses in the domestic and foreign eyeglass markets, and resin lenses have the advantages of light weight, good dyeing property, easy processing and the like compared with glass lenses, and medium and high refractive index optical resin lenses are favored by users with the unique advantages of high light transmittance, ultraviolet resistance, ultra-thinness and the like.

In the lens industry, high refractive index is generally used when the refractive index of the lens is 1.60 or more, medium refractive index is generally used when the refractive index is 1.56 or less, and low refractive index is generally used when the refractive index is 1.56 or less. There are many factors affecting the refractive index of the lens, and due to the structural difference of the lens material itself, the absorption rate of the lens material to light in different bands of visible light is different, so the light transmittance and reflectivity of the lens itself are affected. In order to meet the requirement of optical performance of resin lenses, a film is generally coated on the surface of the resin lenses to reduce the reflection of light and enhance the transmission of light, i.e. an optical antireflection film. The good optical antireflection film can not only enhance the light permeability, but also reduce visual discomfort such as ghost image caused by reflecting stray light. Inorganic materials are often used as optical antireflection film materials, but due to the difference in physical and chemical properties between the substrate of the polymer resin lens and the inorganic material film, the stress of the finished lens is high, the adhesion of the film on the lens substrate is poor, and the high temperature resistance and durability of the coated lens are poor.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a low-stress high-temperature-resistant resin lens and a preparation method thereof, which effectively adopt a special low-stress coating material, obviously reduce the stress of the coated lens, thereby effectively improving the high-temperature resistance and the durability of the coated lens, and further improve the high-temperature resistance of the resin lens by arranging a groove which is invisible to naked eyes on the surface of the resin lens and finely dividing an anti-reflection film layer.

The technical scheme of the invention is realized by the following modes:

the invention provides a low-stress high-temperature-resistant resin lens, which comprises a resin lens substrate, a hardening layer and an antireflection layer which are sequentially arranged; wherein the hardening layer is positioned on the surface of the resin lens substrate, and the antireflection layer is positioned on the surface of the hardening layer;

further, the low-stress high-temperature-resistant resin lens further comprises a waterproof layer, and the waterproof layer is positioned on the surface of the antireflection layer;

further, the surface of the lens is also provided with a grid-shaped groove, and the groove extends to the edge of the lens;

further preferably, the material of the hard layer is organic silicon; preferably, the organosilicon at least contains Ti element; furthermore, the thickness of the hardening layer is 1-5 μm;

further preferably, the antireflection layer comprises a low-stress silicon-magnesium composite oxide layer and ZrO₂A layer and a tin-doped indium oxide (ITO) layer; further preferably, the low-stress silicon-magnesium composite oxide is formed by SiO₂And MgO, in which SiO₂The content of the silicon-magnesium composite oxide accounts for 70 to 95 percent of the mole fraction of the low-stress silicon-magnesium composite oxide; preferably, the thickness of the antireflection layer is 180-400 nm;

further preferably, the waterproof layer is made of a fluorine-containing waterproof material; furthermore, the thickness of the waterproof layer is 4-20 nm;

further preferably, the grid-shaped grooves comprise 1-20 transverse grooves and 1-20 longitudinal grooves; more preferably, the number of the transverse grooves is 2-10, and the number of the longitudinal grooves is 2-10;

further preferably, the depth of the latticed grooves is greater than or equal to the sum of the thicknesses of the waterproof layer and the antireflection layer; more preferably, the depth of the grid-shaped grooves is greater than or equal to the sum of the thicknesses of the waterproof layer and the antireflection layer and is less than 2 μm;

preferably, the width of the grid-shaped groove is 1-50 μm; more preferably, the width of the groove is 2-20 μm;

furthermore, the average reflectivity of the low-stress high-temperature resistant resin lens is less than or equal to 0.5 percent.

The invention also provides a preparation method of the low-stress high-temperature-resistant resin lens, which comprises the following steps:

s1 preparing a stiffening layer: forming a hardening layer on the surface of the resin lens substrate to obtain a resin lens containing the hardening layer;

s2 preparing an antireflection layer: forming the antireflection layer on the surface of the resin lens obtained in S1, that is, obtaining the resin lens containing the antireflection layer, specifically including:

s21: two low-stress silicon-magnesium composite oxide layers and two layers of ZrO are alternately and respectively formed on the surface of the resin lens obtained in step S1₂Layer, i.e. obtained comprising two low-stress silicon-magnesium composite oxide layers and two layers of ZrO₂A resin lens of the layer;

s22: forming a resin lens containing an ITO layer on the surface of the resin lens obtained in step S21;

s23: forming a resin lens containing a low-stress silicon-magnesium composite oxide layer on the surface of the resin lens obtained in step S22;

s3 preparing a waterproof layer: forming a waterproof layer on the surface of the resin lens obtained in the step S23 to obtain a resin lens containing the waterproof layer;

s4 forming grid-like grooves: performing laser transverse and longitudinal cutting on the surface of the resin lens obtained in the step S3 to form a latticed groove, or performing latticed shading on the surface of the resin lens obtained in the step S1 by using tough ultrafine fibers, and performing the steps S2 and S3 to form a latticed groove; preferably, the diameter of the tough ultrafine fibers is 1 to 30 μm; more preferably, the tough microfiber is a core of a single mode optical fiber, and the diameter of the core is 7 μm.

Further, the step S2 specifically includes:

s21: two low-stress silicon-magnesium composite oxide layers and two layers of ZrO are alternately and respectively formed on the surface of the resin lens obtained in step S1₂Layer, i.e. obtained comprising two low-stress silicon-magnesium composite oxide layers and two layers of ZrO₂The resin lens of the layer specifically comprises:

s211, obtaining the surface of the resin lens with the background vacuum degree of less than or equal to 3 × 10 on the surface of the resin lens obtained in S1^-3Pa, the temperature in the coating chamber is 50-70 ℃, an ion source auxiliary process is adopted, and a high-energy electron beam is adopted to heat the silicon-magnesium composite oxide layer at the speed ofCompounding the evaporated silicon and magnesium with oxygenDepositing the chemical layer in a nano-scale molecular form to obtain a resin lens containing a first low-stress silicon-magnesium composite oxide layer;

s212, the surface of the resin lens obtained in S21 is processed in a background vacuum degree of 3 × 10^-3Pa, the temperature in the coating cabin is 50-70 ℃, and ZrO is heated by high-energy electron beams under the condition of an ion source auxiliary process₂At a rate ofThe evaporated ZrO₂Deposited in the form of nanoscale molecules to obtain a layer containing ZrO₂A resin lens of the layer;

s213: repeating the steps S211 and S212 to respectively and alternately form a third layer of low-stress silicon-magnesium composite oxide layer and a fourth layer of ZrO₂Layer, i.e. forming a layer comprising a third silicon-magnesium composite oxide layer and a fourth ZrO layer₂A resin lens of the layer;

s22 obtaining the resin lens surface with the background vacuum degree less than or equal to 3 × 10^-3Pa, the temperature in the coating chamber is 50-70 ℃, and an ion source auxiliary process is adopted, high-energy electron beams are adopted to heat the ITO, and the speed isDepositing the evaporated ITO in a nanoscale molecular form to obtain a resin lens containing a fifth ITO layer;

s23: continuously adopting a vacuum coating process on the surface of the resin lens obtained in the step S22, and repeating the process step S211 to form the resin lens containing the sixth low-stress silicon-magnesium composite oxide layer;

further, the step S3 includes the step of continuing to adopt the vacuum coating process on the surface of the lens obtained in the step S23, wherein the background vacuum degree is less than or equal to 3 × 10^-3Pa, and the temperature in the coating chamber is 50-70 ℃, adopting high-energy electron beams to heat the material at the speed ofDepositing the evaporated fluorine-containing waterproof material on the surface of the substrate in a nano-scale molecular formS23, obtaining the resin lens containing the waterproof layer;

further, in S4, the step of forming the grid-shaped grooves by laser transverse and longitudinal cutting includes: scribing on the surface of the resin lens obtained in the step S3 by adopting an ultraviolet pulse laser light source in a short-focus focusing mode according to the size, the position and the number of preset grooves to form transverse and longitudinal grooves, and then taking out and cleaning the lens to obtain the resin lens;

or further, in S4, with the aid of a microscope, the tough microfiber is first screened in a grid pattern on the surface of the resin lens obtained in S1, and then steps S2 and S3 are performed, and then the tough microfiber is removed to form a grid-shaped groove.

Advantageous effects

1. The silicon-magnesium composite oxide material is adopted to prepare the film layer, so that the stress of the antireflection film layer is reduced, and the durability and the repeatability of the product are improved at the same time:

(1) the stress of the antireflection film layer of the resin lens is obviously reduced:

in one aspect, the present invention reduces stress by altering the antireflective film layer material: the stress of the antireflection film layer of the common resin lens is mainly formed by SiO₂Layer-generated, SiO₂The film layer is easy to form a compact amorphous structure similar to fused quartz during deposition and film forming, so that the film layer generates larger compressive stress. The invention adopts the high-refractive-index material silicon-magnesium composite oxide material with strict molar dosage ratio as the film material to replace SiO₂Film layer capable of effectively destroying SiO₂The compact structure of the silica long chain of the film layer similar to fused quartz enables the structure of the film layer to have the porosity of some MgO materials, and the thermal expansion effect is buffered, so that the stress of the film layer is effectively reduced, and the high temperature resistance and the durability of the product are improved;

on the other hand, the invention reduces the stress by changing the structure of the antireflection film layer: the latticed transverse and longitudinal extremely fine grooves are formed in the surface of the lens, so that the area of a continuous antireflection film on the lens is reduced, the accumulation of surface stress of the lens is reduced, and the high-temperature resistance of the lens is further improved. And the width of the groove is tightly controlled without affecting the appearance of the lens.

(2) Improve the durability and repeatability of the product: when the silicon-magnesium composite oxide film is prepared, an ion source auxiliary process is adopted, and the firmness of the film is effectively improved. Because the film layer material is made of SiO₂And MgO doping, i.e. O in IAD-assisted processes₂When the technological parameters such as flow, voltage, current and the like fluctuate slightly (for example, fluctuation is 15%), the product performance still keeps stable, and the repeatability and the mass production of the product are effectively realized.

Drawings

FIG. 1 is a schematic view of each layer of a low-stress high-temperature-resistant resin lens prepared in example 1 of the present invention

The lens comprises a resin lens substrate 1, a hardening layer 2, an antireflection layer 3 and a waterproof layer 4; wherein, antireflection layer 3 includes: 3-1 of silicon-magnesium composite oxide layer, ZrO₂Layer 3-2, silicon-magnesium composite oxide layer 3-3, ZrO₂Layers 3-4, ITO layers 3-5, and silicon-magnesium composite oxide layers 3-6

FIG. 2 is a schematic view of a trench structure in embodiment 1 of the present invention

Detailed Description

In a specific embodiment, the thicknesses of the layers of the antireflection layer are as follows:

the thickness of the first layer of low-stress silicon-magnesium composite oxide layer is 0-180 nm, preferably 10-60 nm;

the second layer of ZrO₂The thickness of the layer is 10-40 nm, preferably 12-30 nm;

the thickness of the third layer of low-stress silicon-magnesium composite oxide layer is 20-60 nm, preferably 25-40 nm;

the fourth layer of ZrO₂The thickness of the layer is 20-80 nm, preferably 40-70 nm;

the thickness of the fifth layer of ITO layer is 2-10 nm, preferably 5 nm;

the thickness of the sixth layer of low-stress silicon-magnesium composite oxide layer is 60-120 nm, preferably 80-100 nm;

in a specific embodiment, the ITO is formed of In₂O₃And SnO₂Composition In which₂O₃Account for the mass of ITOThe fraction is 90 percent;

in a specific embodiment, the method for preparing the low-stress high-temperature resistant resin lens comprises the following steps:

s1: preparing a hardening layer: immersing a resin lens substrate cleaned by ultrasonic waves into a hardening liquid aqueous solution with the mass percentage of 25-30%, wherein the immersion temperature is 10-20 ℃, after immersing for 5-10 seconds, the solution is pulled out at the speed of 1.0-3.0 mm/s, after drying for 2-4 hours at the temperature of 70-90 ℃, the resin lens substrate is taken out and sent into a drying box for drying and curing, the curing temperature is 110-130 ℃, and the curing time is 120-240 min, so that the resin lens containing a hardening layer is obtained; preferably, the resin lens substrate is immersed into a hardening liquid aqueous solution with the mass percentage of 27%; the dipping temperature is 15 ℃, the time is 5 seconds, the pulling speed is 2.0mm/s, and the drying time at 75 ℃ is 3 hours; preferably, the curing temperature is 120 ℃ and the curing time is 150 min;

s2 preparing an antireflection layer: forming the antireflection layer on the surface of the resin lens obtained in S1, that is, obtaining the resin lens containing the antireflection layer, specifically including:

s21: two low-stress silicon-magnesium composite oxide layers and two layers of ZrO are alternately and respectively formed on the surface of the resin lens obtained in step S1₂Layer, i.e. obtained comprising two low-stress silicon-magnesium composite oxide layers and two layers of ZrO₂The resin lens comprises S211 the resin lens surface obtained in S1 with a vacuum degree of 3 × 10^-3Pa, the temperature in the coating chamber is 50-70 ℃, an ion source auxiliary process is adopted, and a high-energy electron beam is adopted to heat the silicon-magnesium composite oxide layer at the speed ofDepositing the evaporated Si-Mg composite oxide layer in the form of nano-scale molecules to obtain the resin lens containing the first low-stress Si-Mg composite oxide layer, S212, obtaining the resin lens surface at S21 with the vacuum degree of 3 × 10^-3Pa, the temperature in the coating cabin is 50-70 ℃, and ZrO is heated by high-energy electron beams under the condition of an ion source auxiliary process₂At a rate ofThe evaporated ZrO₂Deposited in the form of nanoscale molecules to obtain a layer containing ZrO₂A resin lens of the layer; s213: repeating the steps S211 and S212 to respectively and alternately form a third layer of low-stress silicon-magnesium composite oxide layer and a fourth layer of ZrO₂Layer, i.e. forming a layer comprising a third silicon-magnesium composite oxide layer and a fourth ZrO layer₂A resin lens of the layer;

s22 obtaining the resin lens surface with the background vacuum degree less than or equal to 3 × 10^-3Pa, the temperature in the coating chamber is 50-70 ℃, and an ion source auxiliary process is adopted, high-energy electron beams are adopted to heat the ITO, and the speed isDepositing the evaporated ITO in a nanoscale molecular form to obtain a resin lens containing a fifth ITO layer;

s23: continuously adopting a vacuum coating process on the surface of the resin lens obtained in the step S22, and repeating the process step S211 to form the resin lens containing the sixth low-stress silicon-magnesium composite oxide layer; wherein, in steps S21-S23, the ion source assisted deposition process parameters are: the ion source is a Hall source, and the anode voltage: 90-140V, anode current: 2.5-5A, and the auxiliary gas is O₂The flow rate is 10-30 sccm; preferably, the ion source assisted deposition process parameters are as follows: the ion source is a Hall source, and the anode voltage: 110V, anode current: 4A, the auxiliary gas is O₂The flow rate is 15 sccm;

s3 preparing waterproof layer by vacuum coating process on the surface of the lens obtained in S23 under vacuum degree of 3 × 10^-3Pa, and the temperature in the coating chamber is 50-70 ℃, adopting high-energy electron beams to heat the material at the speed ofDepositing the evaporated fluorine-containing waterproof material on the surface of the resin lens obtained in S23 in a nano-scale molecular form to obtain the resin lens containing a waterproof layer;

s4 forming grid-like grooves: performing laser transverse and longitudinal cutting on the surface of the resin lens obtained in the step S3 to form a latticed groove, or performing latticed shading on the surface of the resin lens obtained in the step S1 by using tough ultrafine fibers, and performing the steps S2 and S3 to form a latticed groove; preferably, the diameter of the tough ultrafine fibers is 1 to 30 μm; more preferably, the tough ultrafine fiber is a core of a single-mode optical fiber, and the diameter of the core is 7 μm;

further, in S4, the step of forming the grid-shaped grooves by laser transverse and longitudinal cutting includes: scribing on the surface of the resin lens obtained in the step S3 by adopting an ultraviolet pulse laser light source in a short-focus focusing mode according to the size, the position and the number of preset grooves to form transverse and longitudinal grooves, and then taking out and cleaning the lens to obtain the resin lens;

or further, in S4, with the aid of a microscope, the tough microfiber is first screened in a grid pattern on the surface of the resin lens obtained in S1, and then steps S2 and S3 are performed, and then the tough microfiber is removed to form a grid-shaped groove.

In one specific embodiment, the silicon-magnesium composite oxide is developed and produced by the company Yokogachi opto-electronic technology, Inc. of Changzhou city₂And MgO, in which SiO₂The mole fraction of the organic solvent is 70-95%, and the specific mixture ratio is shown in examples and comparative examples;

in one embodiment, a resin lens with a refractive index of 1.60 is selected as a substrate, for example, the lens substrate preparation monomer is MR-8 from Mitsui chemical corporation of Japan, hereinafter referred to as "MR-8";

in a specific embodiment, model Z117 of Ito optical industry Co., Ltd (hereinafter referred to as "Z117") is selected as a hardening liquid, and the hardening liquid is selected to prepare the lens of the invention, so that the dense connectivity between the film layers is greatly improved;