CN102269828A - Preparation method of nano-optical anti-fog film - Google Patents
Preparation method of nano-optical anti-fog film Download PDFInfo
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Abstract
The invention relates to the field of chemical engineering and particularly relates to a preparation method of a nano anti-fog film with high hydrophilicity. The novel nano-optical anti-fog film takes a sol in a Si-O-Si reticular structure as a precursor, and an acrylic acid type hydrophilic material is connected on a branched chain of the precursor by adopting the sol-gel method and polyaddition reaction of vinyl double bonds; by adopting the method, the shortcomings that hydrophilic groups are easy to crack and shed on the surface of a substrate can be solved. The nano-optical anti-fog film can be firmly connected with optical glass and other transparent base materials, thereby having high hydrophilicity and high light transmittance.
Description
Technical field
The present invention relates to the materials chemistry field, is the surface modification category of optical material in this field, relates generally to a kind of preparation method and application of novel nano optics antifog film.
Background technology
The formation of water smoke is that the water saturation vapor pressure is reduced to and is lower than airborne steam partial pressure, makes water vapor condense into water droplet and mist formation at body surface because temperature reduces.For example, windshield, bathroom minute surface usually can be tied mist, especially can bring very big inconvenience, even can cause danger for people's production, life because the temperature difference reason produces the mist problem of comparatively significantly tying on the glasses.Therefore, antifog Study on Technology is subjected to people's attention just gradually.
Antifog film is divided into two classes by the ultimate principle of its preparation: 1. water wettability antifog film: reduce substrate surface to the contact angle of water (water contact angle θ＜35 °), make water droplet disperse to form moisture film.2. hydrophobicity antifog film: improve substrate surface to the contact angle of water (water contact angle θ＞100 °), make water droplet can not be adsorbed on material surface.
The present invention adopts the hydrophilic antifogging film as research direction.Reason is that this technology is the most ripe method in antifog material field, present home and abroad.This method is economical and practical, save the energy, anti-fog performance ideal, feasibility are good.Desirable hydrophilic antifogging coating should possess that cost is low, good antifogging effect, longer duration, hardness height, optical material is not had burn into and multiple advantages such as easy to use.The hydrophobicity anti-fog coating exists film forming difficulty, complex manufacturing, technical difficulty is big and manufacturing cost is high all drawbacks by contrast.The most common in the water wettability anti-fog coating with esters of acrylic acid and multipolymer thereof.This material good hydrophilic property, raw material abundance, cost performance height.
" precursor " is a notion commonly used in the domestic and international pharmacy, mainly is meant the chemical group that plays the connection effect.It is comparatively common at medicine, chemical field to add this method of precursor.But application is seldom arranged in the antifog film field.
Sol-gel process (sol-gel), it is a kind of method that is applied to prepare inorganic material.Sol particles generally mostly is macromolecular mass, is difficult to its particle of control at nanoscale.Existing control sol particles is a ultrasonic method in nano level method.Promptly under Ultrasound Instrument sol particles being broken into little particle cluster, is to carry out under pyroreaction, obtains the lack of homogeneity of product, and the character of product is uncontrollable.The sol-gel process advantage is that reaction can be carried out under lower temperature, and process control is convenient, the product structure homogeneous.Molecular group can not be subjected to temperatures involved.Greatly improved the material preparation success ratio.
Preparing the antifog material of macromolecule with compoundization technology in manufacturing process is comparatively ideal development trend.Than the one-component material, compound substance more can satisfy actual needs.Be characterized in compound, make the stronger acting force of formation between each component by multiple material.Can realize performance complement and optimization.Be present state, inside and outside research focus with inorganic/organic composite material again wherein.Its advantage is: (1) is inorganic can realize that with organic phase molecular level or nano-scale are compound, and the interfacial area between the two-phase is very big, and interfacial interaction is strong, make common sharply clearly the interface thicken; (2) optical clear can prepare the hybrid material that contains multiple function ingredients in same residuite, can become the matrix of multiple optically active substance; (3) have certain mechanical stability, pliability and thermal stability, be easy to be processed into material such as film, the fiber etc. of different shape.Because inorganic material and organic polymer nature difference are very big, concentrated two kinds of materials advantage separately after compound, remedy the defective in the material originally, properties of product are excellent more, are the desirable means of development and development of new material.So inorganic/organic composite material has shown wide application prospect in antifog film material field.
Summary of the invention
The present invention is from the shortcoming and the unfavorable problem of anti-fog effect of water wettability acrylic compounds and optical base-substrate connectivity difference, adopt the method that adds the precursor rete, utilize the addition polymerization principle of vinyl double bond that transparent base is carried out surface modification, development can firmly be connected with transparent bases such as optical glass, has the antifog film of high-hydrophilic and transmittance again.
The invention provides a kind of preparation method of optics nanocomposite optical antifog film: prepare precursor colloidal sol earlier, add high hydrophilizing agent then and obtain antifog solution, make antifog film by plated film, detailed process is following steps:
(1) preparation of precursor colloidal sol: in beaker, put into ethyl orthosilicate and vinyltriethoxysilane etc. mole mixed solution, absolute ethyl alcohol, stir, add distilled water afterwards, wherein the mole proportioning of each material is: ethyl orthosilicate: vinyltriethoxysilane: absolute ethyl alcohol: distilled water is (0.5-2.5): (0.5-2.5): (1-5): (0.5-1.5); Hydrochloric acid with 0.08-0.12mol/L is adjusted to 3.4-3.6 with mixed solution pH value then, stirs 3-4h below 60 ℃ and obtains precursor colloidal sol;
(2) preparation of compound antifog solution: measure acrylic acid, methacrylic acid is put into bottle and mixed, and splashes into acrylic acid, methacrylic acid mixed solution in ammoniacal liquor, and with the ice-water bath cooling, reaction generates the mixed solution of ammonium acrylate and ammonium methacrylate; Precursor colloidal sol is placed beaker, splash into the mixed solution of ammonium acrylate and ammonium methacrylate respectively, concentration is the initiator ammonium persulfate solution of 0.02g/mL, density is the Jia Jibingxisuanβ-Qiang Yizhi of 1.074g/mL, wherein acrylic acid: methacrylic acid: ammonium persulfate: the mass percent that Jia Jibingxisuanβ-Qiang Yizhi accounts for total amount is (10-40): (2-8): (0.05-0.5): (3-12); Adding 2-3mL density then is the auxiliary functional group of the methyl methacrylate mixed liquor of 0.944g/mL, and temperature is controlled at 65 ℃, when treating that solution viscosity changes, rapidly solution is put into cooling bath and cools off, and obtains antifog composite solution;
(3) optical base-substrate pre-service;
(4) plated film and curing.
The preparation method of a kind of optics nanocomposite optical antifog film provided by the invention, concrete preparation process is following steps:
(1) preparation of precursor colloidal sol: in beaker, put into ethyl orthosilicate that 28mL density is 0.93g/mL (TEOS) and 26.3mL density and be 0.903g/mL vinyltriethoxysilane etc. mole mixed solution, 4.6mL density be the absolute ethyl alcohol (ETOH) of 0.789g/mL, stir, add the 1.8mL distilled water afterwards, with the hydrochloric acid of 0.1mol/L mixed solution pH value being adjusted to 3.5,60 ℃ stirs 3h down and obtains precursor colloidal sol;
(2) preparation of compound antifog solution: the methacrylic acid (MA) of measuring the acrylic acid that 38mL density is 1.05g/mL (AC), 5.9mL density and be 1.01g/mL is put into bottle and is mixed, in ammoniacal liquor, splash into acrylic acid, methacrylic acid mixed solution, and, react the mixed solution that generates ammonium acrylate and ammonium methacrylate with the ice-water bath cooling; The 3rd step, precursor colloidal sol is placed beaker, splash into the mixed solution of 40mL ammonium acrylate and ammonium methacrylate respectively, 5mL concentration is initiator ammonium persulfate (AP) solution of 0.02g/mL, 11mL density is the Jia Jibingxisuanβ-Qiang Yizhi (HEMA) of 1.074g/mL, the auxiliary functional group of methyl methacrylate (MMA) mixed liquor that 2mL density is 0.944g/mL, temperature is controlled at 65 ℃, when treating that solution viscosity changes, rapidly solution is put into cooling bath and cool off, obtain antifog composite solution;
(3) optical base-substrate pre-service;
(4) plated film and curing;
The precursor that is used for the preparation method of above-mentioned nanocomposite optical antifog film, this precursor are the Si-O-Si reticulate texture.Adopt conventional sol-gel process (sol-gel) to prepare this precursor, carry out the colloid modification by adjusting preparation parameter, the sol particles size Control in nano level scope, is reached nanoscale even molecular level level, have better rete physical property after rete is solidified.
In the technical scheme of the present invention, the technology that precursor is connected with water wetted material adopts the addition polymerization method to make on the unsaturated carbon-carbon double bond of acrylic compounds water wetted material and the precursor side chain-CH=CH
2Key connects.This method has guaranteed water wetted material and precursor connection stability, has solved the shortcoming that water wetted material comes off from the optical element surface easily.
Description of drawings
Fig. 1 is antifog composite solution grain-size graph, and antifog composite solution grain is 265.0 ± 43.8nm.
Fig. 2 is the anti-reflection antifog film sem photograph of nanometer.
Fig. 3 is the anti-reflection antifog film light transmittance curve of nanometer, light transmittance curve behind the a-plated film; Light transmittance curve before the b-plated film.
Fig. 4 is a rete water wettability test pattern, water contact angle before the a-plated film; Water contact angle behind the b-plated film.
Fig. 5 is the infrared spectrum of precursor.
Fig. 6 is the precursor X-ray diffractogram.
Fig. 7 is the infrared spectrum of the anti-reflection antifog film of nanometer.
Fig. 8 is a nano-hydrophilic antifog film X-ray diffractogram.
Specific implementation method
The prescription screening:
Explore in the experiment and find, the cancellated material of Si-O-Si can firm attachment on the clear optical glass surface.Can further in the cancellated material of Si-O-Si, add multiple hydrophilic radical on this basis and realize the rete anti-fog function.Ethyl orthosilicate (TEOS) and vinyltriethoxysilane (A-151) are all organosilicon material.In course of reaction, generate the Si-O-Si reticulate texture, link firmly with the clear optical glass surface.A-151 is that an end has Si-O-C
2H
5Key, the other end has Si-CH=CH
2The colourless transparent liquid of key.After opening, vinyl double bond can connect hydrophilic radical.
Reagent ethyl orthosilicate of the present invention (TEOS) and vinyltriethoxysilane (A-151) all have Si-O-C
2H
5Silane structure, but owing to have Si-CH=CH essential in the experiment among the A-151
2Key if ratio crosses that I haven't seen you for ages influences the quantity of unsaturated double-bond on the reticulate texture side chain in material, and then influences the link of precursor and hydrophilic radical.Therefore, experiment selects for use mole mixed solutions such as TEOS, A-151 as reaction material.Could guarantee to make the precursor rete like this and on the Si-O-Si structure, be connected with enough unsaturated-CH=CH
2Key.
Precursor preparation prescription screens with conjugation as the optimum formula evaluation index.
Conjugation is an important indicator of estimating the precursor quality, and the factor that influences the rete bond quality is a lot, chooses 3 bigger principal elements of evaluation index influence, and each factor is got 3 levels, sees Table 1, presses L
9(3
4) arrange orthogonal experiment, every group of experiment carried out 2 times at random, with the minimizing experimental error, the analysis of averaging, and best proportioning carried out Quality Identification.
Table 1 precursor factor level table
Table 2L
9(3
4) orthogonal experiment and result
Table 3 conjugation analysis of variance table
F
0.05(2，2)＝19.00
Prescription screening is the result show, best proportioning is A
3B
3C
2That is, the mixed solution consumption of TEOS and vinyltriethoxysilane is 2.5mol, and the ETOH consumption is 5mol, H
2The O consumption is 1mol.
The antifog formulations prepared from solutions prescription screening of nano-hydrophilic is that evaluation index is as the optimum formula evaluation index with conjugation and water wettability.
Conjugation and water wettability are to estimate the important indicator of precursor quality, and the factor that influences the rete bond quality is a lot, choose 4 bigger principal elements of evaluation index influence, and each factor is got 4 levels, sees Table 4, presses L
16(4
5) arrange orthogonal experiment, every group of experiment carried out 2 times at random, with the minimizing experimental error, the analysis of averaging, and best proportioning carried out Quality Identification.
The antifog solution factor level of table 4 nano-hydrophilic table
Remarks: other percentage composition is precursor colloidal sol and the auxiliary functional group of methyl methacrylate (MMA) mixed liquor.
Table 5L
16(4
5) orthogonal experiment and result
Table 6 conjugation analysis of variance table
F
0.05＝9.280
Table 7 water wettability analysis of variance table
F
0.05＝9.280
Prescription screening is the result show, best proportioning is A
4B
3C
2D
4Be that the acrylic acid consumption is 40%, the methacrylic acid consumption is 6%, and the ammonium persulfate consumption is 0.1%, and the Jia Jibingxisuanβ-Qiang Yizhi consumption is 12%, and all the other are precursor colloidal sol and the auxiliary functional group of methyl methacrylate (MMA) mixed liquor.
Embodiment 2
Reagent
Instrument
Step 1: antifog formulations prepared from solutions
(1) preparation of precursor colloidal sol: in beaker, put into 28mL, density is ethyl orthosilicate (TEOS) and the 26.3mL of 0.93g/mL, density be 0.903g/mL vinyltriethoxysilane (A-151) etc. mole mixed solution, 4.6mL density be the absolute ethyl alcohol (ETOH) of 0.789g/mL, stir, add the 1.8mL distilled water afterwards, with the hydrochloric acid of 0.1mol/L mixed solution pH value being adjusted to 3.5,60 ℃ stirs 3h down and obtains precursor colloidal sol;
(2) preparation of compound antifog solution: the methacrylic acid (MA) of measuring the acrylic acid that 38mL density is 1.05g/mL (AC), 5.9mL density and be 1.01g/mL is put into bottle and is mixed, in ammoniacal liquor, splash into acrylic acid, methacrylic acid mixed solution, and, react the mixed solution that generates ammonium acrylate and ammonium methacrylate with the ice-water bath cooling; The 3rd step, precursor colloidal sol is placed beaker, splash into the mixed solution of 40mL ammonium acrylate and ammonium methacrylate respectively, 5mL concentration is initiator ammonium persulfate (AP) solution of 0.02g/mL, 11mL density is Jia Jibingxisuanβ-Qiang Yizhi (HEMA), the 2mL of 1.074g/mL, density is the auxiliary functional group of methyl methacrylate (MMA) mixed liquor of 0.944g/mL, temperature is controlled at 65 ℃, when treating that solution viscosity changes, rapidly solution is put into cooling bath and cool off, obtain antifog composite solution;
(3) optical base-substrate is handled
Substrate is put into the 500mL beaker, is 3: 7 the hydrogen peroxide and the concentrated sulphuric acid to wherein adding the 100mL volume ratio.To mix washing lotion afterwards 70 ℃ of following heat treated, no bubble produces in beaker.Subsequently substrate is reduced to room temperature, after putting into distilled water and soaking 8min, use soaked in absolute ethyl alcohol 4min again, dry up, obtain clean substrate with nitrogen.
(4) plated film and curing
Just pretreated transparent optical material is invaded in the solution, takes out after leaving standstill 10min, dries up under the nitrogen.Put in 25 ℃ of drying bakers, and slowly evenly heat up.Be warmed up to 100 ℃, constant temperature 20min.Take out material and treat that descend back plated film and curing of temperature finishes.
Step 4: phenetic analysis
(1) grain diameter measurement: adopt the Malvern Ma Erwen Zetasiaer 1000HS-A of company laser particle size analyzer, the particle diameter of antifog solution is: (265.0 ± 43.8) nm.As shown in Figure 1.
(2) film layer structure is measured: adopt and sweep the Japanese Jeol JSM-6060LV of company and retouch electron microscope, show that film surface is smooth, be connected firmly, evenly.As shown in Figure 2.
(3) determination of light transmittance: adopt the UV-2550PC of the Feng company ultraviolet spectrophotometer test of SHIMADZU island, transmittance is 94.6%.As shown in Figure 3.
(4) water contact angle measurement: the angle is adopted and is gone up the marine POWEREACH JC2000C of digital technology company limited contact angle tester test in morning, and recording water contact angle is 14.5 °, as shown in Figure 4.
(5) primary structure of precursor composition is measured: adopt Switzerland Bruker company's T ensor 27 infrared spectrometers and the Japanese Rigaku D/Max 2550X of company x ray diffractometer x.As Fig. 5, shown in Figure 6.Contrast Fig. 5 Fig. 6, can draw the primary structure of this precursor, as shown in table 1:
The infrared absorption peak position of table 1 main functional group
(6) primary structure of antifog film composition is measured: adopt Switzerland Bruker company's T ensor 27 infrared spectrometers and the Japanese Rigaku D/Max 2550X of company x ray diffractometer x.As Fig. 7, shown in Figure 8.Contrast Fig. 5 Fig. 6, can draw the primary structure of antifog film, as shown in table 2:
The infrared absorption peak position of table 2 main functional group
(7) conjugation detects: adopt GB/T 9286-1998 " rete is drawn the lattice experiment ", the adhesion of qualitative determination rete.With edge is that the hard aluminium alloy cutter at 30 ° of angles is at about 100mm
2Film surface on mark 100 areas and be approximately 1mm
2Grid, and make each lattice independent separately, be overlying on the coating surface with adhesive tape again, press and tear adhesive tape after even, observe remaining number of squares on the rete, conjugation numerical value represents with centesimal system,
The experiment triplicate is averaged.Average conjugation is 95.1%.
(8) hardness measurement: adopt GB 6739-86 " hardness of film pencil determination method ".Prepare one group of China's board advanced drawing pencil, from 6H to 6B.With penknife pencil sharper is gone out long 5.0～6.0mm pen core, beat the lead for retractable pencil end face with sand paper then, smooth up to end face, clear-cut margin.Hold pencil and model is at 45, advance with 1mm/s speed.From the hardest pencil, every grade of pencil is drawn 5 roads, until find out do not scratch the pencil of filming till.Film hardness is 6H.
(9) fastness to rubbing detects: the optical mirror slip that the surface is coated with the optimal proportion antifog film, be placed on 1h in 50 ℃ of constant temperature drying casees, put into-5 ℃ refrigerating chamber 1h after the taking-up, then it is invaded 20min in the clear water, taking out the back cleans with shaggy cloth, operation repeats 3 times and observes the rete degree of wear, no scratch, and wearing quality is good.
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Claims (4)
1. the preparation method of a nanocomposite optical antifog film is characterized in that, preparation precursor colloidal sol adds high hydrophilizing agent then and obtains compound antifog solution earlier, makes antifog film by plated film, and detailed process is following steps:
(1) preparation of precursor colloidal sol: in beaker, put into ethyl orthosilicate and vinyltriethoxysilane etc. mole mixed solution, absolute ethyl alcohol, stir, add distilled water afterwards, wherein the mole proportioning of each material is: ethyl orthosilicate: vinyltriethoxysilane: absolute ethyl alcohol: distilled water is (0.5-2.5): (0.5-2.5): (1-5): (0.5-1.5); Hydrochloric acid with 0.08-0.12mol/L is adjusted to 3.4-3.6 with mixed solution pH value then, stirs 3-4h below 60 ℃ and obtains precursor colloidal sol;
(2) preparation of compound antifog solution: measure acrylic acid, methacrylic acid is put into bottle and mixed, and splashes into acrylic acid, methacrylic acid mixed solution in ammoniacal liquor, and with the ice-water bath cooling, reaction generates the mixed solution of ammonium acrylate and ammonium methacrylate; Precursor colloidal sol is placed beaker, splash into the mixed solution of ammonium acrylate and ammonium methacrylate respectively, concentration is the initiator ammonium persulfate solution of 0.02g/mL, density is the Jia Jibingxisuanβ-Qiang Yizhi of 1.074g/mL, wherein acrylic acid: methacrylic acid: ammonium persulfate: the mass percent that Jia Jibingxisuanβ-Qiang Yizhi accounts for total amount is (10-40): (2-8): (0.05-0.5): (3-12); Adding 2-3mL density then is the auxiliary functional group of the methyl methacrylate mixed liquor of 0.944g/mL, and temperature is controlled at 65 ℃, when treating that solution viscosity changes, rapidly solution is put into cooling bath and cools off, and obtains antifog composite solution;
(3) optical base-substrate pre-service;
(4) plated film and curing.
2. according to the preparation method of the described a kind of nanocomposite optical antifog film of claim 1, it is characterized in that detailed process is following steps:
(1) preparation of precursor colloidal sol: in beaker, put into vinyltriethoxysilane that ethyl orthosilicate that 28mL density is 0.93g/mL and 26.3mL density is 0.903g/mL etc. mole mixed solution, 4.6mL density be the absolute ethyl alcohol of 0.789g/mL, stir, add the 1.8mL distilled water afterwards, with the hydrochloric acid of 0.1mol/L mixed solution pH value being adjusted to 3.5,60 ℃ stirs 3h down and obtains precursor colloidal sol;
(2) preparation of compound antifog solution: measure acrylic acid that 38mL density is 1.05g/mL, methacrylic acid that 5.9mL density is 1.01g/mL is put into bottle and mixed, in ammoniacal liquor, splash into acrylic acid, methacrylic acid mixed solution, and, react the mixed solution that generates ammonium acrylate and ammonium methacrylate with the ice-water bath cooling; The 3rd step, precursor colloidal sol is placed beaker, splash into the mixed solution of 40mL ammonium acrylate and ammonium methacrylate respectively, 5mL concentration is the initiator ammonium persulfate solution of 0.02g/mL, 11mL density is the Jia Jibingxisuanβ-Qiang Yizhi of 1.074g/mL, the auxiliary functional group of the methyl methacrylate mixed liquor that 2mL density is 0.944g/mL, and temperature is controlled at 65 ℃, when treating that solution viscosity changes, rapidly solution is put into cooling bath and cool off, obtain antifog composite solution;
(3) optical base-substrate pre-service;
(4) plated film and curing.
3. the precursor that is used for the preparation method of claim 1 nanocomposite optical antifog film, it is characterized in that, this precursor is the Si-O-Si reticulate texture, its preparation method is: in beaker, put into ethyl orthosilicate and vinyltriethoxysilane etc. mole mixed solution, absolute ethyl alcohol, stir, add distilled water afterwards, the mole proportioning of each material is: ethyl orthosilicate: vinyltriethoxysilane: absolute ethyl alcohol: distilled water=(0.5-2.5): (0.5-2.5): (1-5): (0.5-1.5); Hydrochloric acid with 0.08-0.12mol/L is adjusted to 3.4-3.6 with mixed solution pH value then, stirs 3-4h below 60 ℃ and obtains precursor colloidal sol.
4. according to the precursor among the preparation method of the described nanocomposite optical antifog film of claim 3, it is characterized in that, the preparation method of precursor be in beaker, put into vinyltriethoxysilane that ethyl orthosilicate that 28mL density is 0.93g/mL and 26.3mL density is 0.903g/mL etc. mole mixed solution, 4.6mL density be the absolute ethyl alcohol of 0.789g/mL, stir, add the 1.8mL distilled water afterwards, with the hydrochloric acid of 0.1mol/L mixed solution pH value being adjusted to 3.5,60 ℃ stirs 3h down and obtains precursor colloidal sol.
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| CN104019326A (en) * | 2014-06-11 | 2014-09-03 | 中国石油大学(北京) | Positioning system, device and method of pipeline cleaning device |
| CN104558661A (en) * | 2014-12-18 | 2015-04-29 | 盐城工学院 | Antifogging resin optical lens and preparation method thereof |
| CN105629351A (en) * | 2015-12-31 | 2016-06-01 | 奥特路（漳州）光学科技有限公司 | Lamp cover for blue light filtering, sterilization and reflection resisting and manufacturing method thereof |
| CN105669922A (en) * | 2016-03-10 | 2016-06-15 | 华侨大学 | Preparation method of strawberry type polymer/silicon dioxide nano-composite particles |
| CN106477913A (en) * | 2016-10-21 | 2017-03-08 | 常州亚环环保科技有限公司 | A kind of preparation method of persistent form compound anti-mist film |
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| CN112110654A (en) * | 2020-09-25 | 2020-12-22 | 常州大学 | Preparation method and application of optical anti-reflection antifogging film |
| CN112505947A (en) * | 2020-12-24 | 2021-03-16 | 重庆潮汐眼镜有限公司 | Processing method of glasses lens |
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| CN107937165A (en) * | 2017-11-15 | 2018-04-20 | 永嘉姜君科技有限公司 | A kind of spectacle antifogging cleaning solution and preparation method thereof |
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| CN112110654B (en) * | 2020-09-25 | 2022-07-05 | 常州大学 | Preparation method and application of optical anti-reflection antifogging film |
| CN112505947A (en) * | 2020-12-24 | 2021-03-16 | 重庆潮汐眼镜有限公司 | Processing method of glasses lens |
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