CN102269828B - 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 fit saturated 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 mirror surface usually can be tied mist, especially can because the temperature difference reason produces the mist problem of comparatively significantly tying, bring very large inconvenience, even can cause danger for people's production, life on the glasses.Therefore, the research of antifog technology is subject 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 of the antifog Material Field in present home and abroad.The method is economical and practical, save the energy, anti-fog performance is desirable, feasibility is good.Desirable hydrophilic antifogging coating should possess that cost is low, good antifogging effect, longer duration, hardness are high, to optical material without burn into and the multiple advantages such as easy to use.The hydrophobicity anti-fog coating exists film forming difficulty, complex manufacturing, technical difficulty is large and manufacturing cost is high all drawbacks by contrast.The most common with esters of acrylic acid and multipolymer thereof in the water wettability anti-fog coating.This material good hydrophilic property, raw material is sufficient, and cost performance is high.
" precursor " is a concept commonly used in the domestic and international pharmacy, mainly refers to play the chemical group of connection function.It is comparatively common at medicine, chemical field to add this method of precursor.But in the antifog film field application is arranged seldom.
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 ultrasonic method in nano level method.Namely 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 subject to temperatures involved.Greatly improve material and be prepared into power.
Preparing the antifog material of macromolecule with the Composite 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 by multiple material, make the stronger acting force of formation between each component.Can realize performance complement and optimization.Wherein again take inorganic/organic composite material as present state, inside and outside study hotspot.Its advantage is: (l) inorganic phase and organic phase can realize that molecular level or nano-scale are compound, and the interfacial area between the two-phase is very large, and interfacial interaction is strong, make common sharply clearly the interface thicken; (2) optical clear can prepare the hybrid material that contains the several functions component 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 various shapes.Because inorganic material and organic polymer nature difference are very big, the compound rear bi-material advantage separately of having concentrated remedies the defective in the script material, and properties of product are more excellent, are the desirable means of development and development of new material.So inorganic/organic composite material has shown wide application prospect at the antifog film Material Field.
Summary of the invention
The present invention is from water wettability acrylic compounds and optical base-substrate connectivity poor shortcoming and the undesirable problem of anti-fog effect, 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 be connected transparent base firmly to connect with optical glass, has again the antifog film of high-hydrophilic and transmittance.
The invention provides a kind of preparation method of optics nanocomposite optical antifog film: prepare first precursor colloidal sol, then add high hydrophilizing agent 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 afterwards distilled water, 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); Then the hydrochloric acid with 0.08-0.12mol/L is adjusted to 3.4-3.6 with mixed solution pH value, stirs 3-4h below 60 ℃ and obtains precursor colloidal sol;
(2) preparation of compound anti-mist solution: measure acrylic acid, methacrylic acid is put into bottle and mixed, in ammoniacal liquor, splash into acrylic acid, methacrylic acid mixed solution, and with the ice-water bath cooling, react the mixed solution that generates ammonium acrylate and ammonium methacrylate; Precursor colloidal sol is placed beaker, splash into respectively the mixed solution of ammonium acrylate and ammonium methacrylate, concentration is the initiator ammonium persulfate solution of 0.02g/mL, density is the β-hydroxyethyl methacry-late of 1.074g/mL, wherein acrylic acid: methacrylic acid: ammonium persulfate: the mass percent that β-hydroxyethyl methacry-late accounts for total amount is (10-40): (2-8): (0.05-0.5): (3-12); Then adding 2-3mL density 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 compound anti-mist 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 the 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 afterwards the 1.8mL distilled water, with the hydrochloric acid of 0.1mol/L mixed solution pH value is adjusted to 3.5,60 ℃ of lower 3h of stirring and obtains precursor colloidal sol;
(2) preparation of compound anti-mist 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 with the ice-water bath cooling, react the mixed solution that generates ammonium acrylate and ammonium methacrylate; The 3rd step, precursor colloidal sol is placed beaker, splash into respectively the mixed solution of 40mL ammonium acrylate and ammonium methacrylate, 5mL concentration is initiator ammonium persulfate (AP) solution of 0.02g/mL, 11mL density is the β-hydroxyethyl methacry-late (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 compound anti-mist solution;
(3) optical base-substrate pre-service;
(4) plated film and curing;
Be used for the preparation method's of above-mentioned nanocomposite optical antifog film precursor, this precursor is 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 coating physical performance 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.The method has guaranteed the stability that water wetted material is connected with precursor, has solved the shortcoming that water wetted material comes off from the optical element surface easily.
Description of drawings
Fig. 1 is compound anti-mist solution grain-size graph, and compound anti-mist solution grain is 265.0 ± 43.8nm.
Fig. 2 is the anti-reflection antifog film scanning electron microscope (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 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 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 realization rete anti-fog function on this basis.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 is with Si-O-C
2H
5Key, the other end is with 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 affects the quantity of unsaturated double-bond on the reticulate texture side chain in material, and then affects the link of precursor and hydrophilic radical.Therefore, experiment selects the mole mixed solutions such as TEOS, A-151 as reaction material.Like this guarantee make the precursor rete 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 the important indicator of estimating the precursor quality, and the factor that affects the rete bond quality is a lot, chooses 3 larger principal elements of evaluation index impact, and each factor is got 3 levels, sees Table 1, presses L
9(3
4) arranging 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 screening of the antifog solution of nano-hydrophilic preparation prescription take conjugation and water wettability as evaluation index as the optimum formula evaluation index.
Conjugation and water wettability are to estimate the important indicator of precursor quality, and the factor that affects the rete bond quality is a lot, choose 4 larger principal elements of evaluation index impact, and each factor is got 4 levels, sees Table 4, presses L
16(4
5) arranging 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 β-hydroxyethyl methacry-late 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 solution preparation
(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 afterwards the 1.8mL distilled water, with the hydrochloric acid of 0.1mol/L mixed solution pH value is adjusted to 3.5,60 ℃ of lower 3h of stirring and obtains precursor colloidal sol;
(2) preparation of compound anti-mist 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 with the ice-water bath cooling, react the mixed solution that generates ammonium acrylate and ammonium methacrylate; The 3rd step, precursor colloidal sol is placed beaker, splash into respectively the mixed solution of 40mL ammonium acrylate and ammonium methacrylate, 5mL concentration is initiator ammonium persulfate (AP) solution of 0.02g/mL, 11mL density is β-hydroxyethyl methacry-late (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 compound anti-mist solution;
(3) optical base-substrate is processed
Substrate is put into the 500mL beaker, to wherein adding hydrogen peroxide and the concentrated sulphuric acid that the 100mL volume ratio is 3:7.To mix afterwards washing lotion 70 ℃ of lower heat treated, until in the beaker without Bubble formation.Subsequently substrate is down to room temperature, after putting into distilled water and soaking 8min, uses again soaked in absolute ethyl alcohol 4min, dry up with nitrogen, obtain clean substrate.
(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.Taking out material plated film and curing behind drop in 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 test of the SHIMADZU Shimadzu UV-2550PC of company ultraviolet spectrophotometer, transmittance is 94.6%.As shown in Figure 3.
(4) water contact angle measurement: the upper marine POWEREACH JC2000C of digital technology company limited contact angle tester test in morning is adopted at the angle, 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.Such 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.Such 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.Be that the hard aluminium alloy cutter at 30 ° of angles is at about 100mm with edge
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 that with centesimal system the experiment triplicate is averaged.Average conjugation is 95.1%.
(8) Determination of Hardness: 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, then beat the lead for retractable pencil end face with sand paper, until end face is smooth, 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, does not scratch till the pencil of filming until find out.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 temp. drying boxes, put into-5 ℃ refrigerating chamber 1h after the taking-up, then it is invaded 20min in the clear water, clean with shaggy cloth after taking out, operation repeats 3 times and observes the rete degree of wear, and without scratch, wearing quality is good.
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Claims (4)
1. the preparation method of a nanocomposite optical antifog film is characterized in that, prepares first precursor colloidal sol, then adds high hydrophilizing agent and obtains compound anti-mist solution, 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 afterwards distilled water, 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); Then the hydrochloric acid with 0.08-0.12mol/L is adjusted to 3.4-3.6 with mixed solution pH value, stirs 3-4h below 60 ℃ and obtains precursor colloidal sol;
(2) preparation of compound anti-mist solution: measure acrylic acid, methacrylic acid is put into bottle and mixed, in ammoniacal liquor, splash into acrylic acid, methacrylic acid mixed solution, and with the ice-water bath cooling, react the mixed solution that generates ammonium acrylate and ammonium methacrylate; Precursor colloidal sol is placed beaker, splash into respectively the mixed solution of ammonium acrylate and ammonium methacrylate, concentration is the initiator ammonium persulfate solution of 0.02g/mL, density is the β-hydroxyethyl methacry-late of 1.074g/mL, wherein acrylic acid: methacrylic acid: ammonium persulfate: the mass percent that β-hydroxyethyl methacry-late accounts for total amount is (10-40): (2-8): (0.05-0.5): (3-12); Then adding 2-3mL density 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 compound anti-mist solution;
(3) optical base-substrate pre-service;
(4) plated film and curing.
2. the preparation method of described a kind of nanocomposite optical antifog film according to claim 1 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 afterwards the 1.8mL distilled water, with the hydrochloric acid of 0.1mol/L mixed solution pH value is adjusted to 3.5,60 ℃ of lower 3h of stirring and obtains precursor colloidal sol;
(2) preparation of compound anti-mist 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 with the ice-water bath cooling, react the mixed solution that generates ammonium acrylate and ammonium methacrylate; The 3rd step, precursor colloidal sol is placed beaker, splash into respectively the mixed solution of 40mL ammonium acrylate and ammonium methacrylate, 5mL concentration is the initiator ammonium persulfate solution of 0.02g/mL, 11mL density is the β-hydroxyethyl methacry-late 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 compound anti-mist 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 afterwards distilled water, 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); Then the hydrochloric acid with 0.08-0.12mol/L is adjusted to 3.4-3.6 with mixed solution pH value, stirs 3-4h below 60 ℃ and obtains precursor colloidal sol.
4. the precursor among the preparation method of described nanocomposite optical antifog film according to 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 afterwards the 1.8mL distilled water, with the hydrochloric acid of 0.1mol/L mixed solution pH value is adjusted to 3.5,60 ℃ of lower 3h of stirring and obtains precursor colloidal sol.
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| CN103910835A (en) * | 2014-03-31 | 2014-07-09 | 永星化工(上海)有限公司 | Preparation method of long-acting hydrophilic antifog light-cured resin |
| CN104019326B (en) * | 2014-06-11 | 2016-03-30 | 中国石油大学(北京) | A kind of pipeline cleaner navigation system, device and method |
| 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 |
| CN105669922B (en) * | 2016-03-10 | 2018-03-09 | 华侨大学 | The preparation method of strawberry type polymer/gold/silicon dioxide nano complex particle |
| 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 |
| CN107298733B (en) * | 2017-07-20 | 2020-05-12 | 东莞南玻太阳能玻璃有限公司 | Template agent for anti-reflection coating liquid and preparation method and application thereof |
| 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 |
| CN109535785A (en) * | 2018-11-27 | 2019-03-29 | 东莞市和域战士纳米科技有限公司 | A kind of super-hydrophobic transparent waterproof membrane and preparation method thereof |
| 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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| 李坚等.表面改性对光学眼镜膜增透防雾效果的影响.《中国组织工程研究与临床康复》.2010,第14卷(第8期),1418-1421. |
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