CN116017967A - Mask liquid and preparation method of random crack template and electromagnetic shielding optical window - Google Patents
Mask liquid and preparation method of random crack template and electromagnetic shielding optical window Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
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Abstract
The invention belongs to the technical field of electromagnetic shielding optical windows, and particularly relates to a mask liquid, a random crack template and a preparation method of an electromagnetic shielding optical window. The preparation method of the mask liquid comprises the following steps: and (3) preserving heat of a mixed solution of the monomer mixture, the emulsifier and the initiator at 80-85 ℃, cooling, adjusting the pH value to be neutral after cooling to room temperature, filtering with 400-500 mesh filter cloth or a filter membrane, and collecting filtrate as mask liquid. The preparation method of the random crack template and the electromagnetic shielding optical window is to prepare the mask liquid. The invention can solve the problems that the machining cannot be realized and the laser etching cost is high in the processing and manufacturing of the metal mesh electromagnetic shielding optical window with the random crack width of less than 3mm at present.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding optical windows, and particularly relates to mask liquid for preparing an electromagnetic shielding optical fiber window, a corresponding random crack template and a preparation method of the electromagnetic shielding optical window.
Background
The electromagnetic shielding optical window is a core functional element for ensuring the normal operation of photoelectric instruments and equipment in microwave and electromagnetic pulse radiation environments, such as an instrument display screen of electronic instruments and meters for various purposes, windows of airplanes and vehicles, a photoelectric detector system and the like.
The metal grid type electromagnetic shielding optical window is a transparent optical window device for attenuating electromagnetic wave radiation through the metal grid. The realization method of the electromagnetic shielding performance of the metal mesh grid type electromagnetic shielding optical window is mainly to plate the metal mesh grid with good conductive performance on the optical glass substrate. Common preparation methods for regular shapes include ultraviolet lithography, ion beam etching, chemical etching, laser direct writing, electroplating, self-assembly, and the like. These preparation methods all require expensive writing equipment and have complicated processes.
Compared with the method, the random crack template method has the unique advantages of short process flow, no need of large-scale precise equipment, low cost and the like, and solves the problems of complexity, high equipment dependence and the like of the traditional metal grid film process.
The preparation method of the random crack template comprises the steps of coating mask liquid on optical window glass to form a mask layer, generating proper cracks (comprising a plurality of cracks with different lengths and randomly distributed to form a plurality of grids) on the surface of the optical glass after the mask layer is cracked, plating a metal grid in the cracks, and removing the mask layer to form the template of the plated metal grid, wherein the template is shown in fig. 1.
The design and preparation process of the random crack template plays a vital role in electromagnetic shielding performance, and the width and depth of cracks on the template directly influence the line width and thickness of the subsequent metal grid, so that the electromagnetic shielding capacity of the metal grid is influenced, and therefore, the method is an important link in the random electromagnetic shielding grid forming process.
The existing preparation process of the random crack template mainly comprises a spin coating method, a lifting method or a spraying method. In the process, the crack width, the uniformity of the crack width, the communication of the crack and the like of the crack template,The factors of the main influence of the grid size, the grid distribution uniformity, the template flatness and other performances are that the mask liquid, the property of the mask liquid mainly determines the performance of forming a crack template, and the common mask liquid is TiO 2 Sol, gelatin, crack nail polish containing acrylic resin, egg white, etc.
For example, in the prior art CN201310122824.1 and in the literature Uniformself-forming metallic network as a high-performance transparent conductiveelectrode microcrystalline TiO is described 2 Crack template for transparent conductive electrode manufactured by mask liquid and TiO 2 The template removing process adopts a mechanical friction method. The mechanical friction process has great control difficulty, and may cause incomplete template removal or excessive friction, which may affect the light transmittance and optical quality of the substrate.
In CN201510262998.7, crack nail polish CA600, CN201910315144.9 and CN202210565512.7 containing acrylic resin are adopted to prepare a mask plate by using aqueous acrylic emulsion, and because the composition content of a commercially available product is fixed, the adjustable parameters and the range are very limited when the crack template is prepared, the crack line width and the period parameters of the prepared crack template are also relatively fixed, and the uniformity of the crack template grid and the crack communication quality are relatively low, the metal grid product processed by the template has great limitation on the use of photoelectric equipment with high imaging quality requirement.
In summary, the existing random crack template has lower uniformity of crack template grids and lower quality of crack communication, so that the light transmittance and optical quality of a later window are poor.
Disclosure of Invention
In view of the drawbacks or shortcomings of the prior art, one aspect of the present invention is to provide a masking liquid.
Therefore, the preparation method of the mask liquid provided by the invention comprises the following steps: preserving heat of a mixed solution of the monomer mixture, the emulsifier and the initiator at 80-85 ℃, cooling, adjusting the pH value to be neutral after cooling to room temperature, filtering with 400-500 mesh filter cloth or a filter membrane, and collecting filtrate as mask liquid;
the monomer mixture is a mixture of methyl methacrylate, n-butyl acrylate, hydroxypropyl acrylate, methacrylic acid and styrene;
the emulsifier is an aqueous solution of allyloxy-2-hydroxy propane sodium sulfonate and dodecylphenol polyoxyethylene ether, or an aqueous solution of allyloxy-fatty alcohol oxyvinyl ether sodium sulfonate and dodecylphenol polyoxyethylene ether, or an aqueous solution of disodium glycolate and dodecylphenol polyoxyethylene ether;
the initiator is an aqueous solution of 1, 3-tetramethyl peroxy-butyl-2-ethylhexanoate.
Alternatively, the preparation method of the mixed solution of the monomer mixture, the emulsifier and the initiator comprises the following steps: mixing the emulsifier and a part of the monomer mixture, regulating the pH value to be neutral, uniformly mixing, heating to 70-75 ℃, adding a part of the initiator, continuously heating to 75-80 ℃, preserving heat, adding the rest of the monomer mixture and the rest of the initiator, mixing, and preserving heat. Further alternatively, the partial amount of initiator is added by means of dropwise addition; the rest amount of the monomer mixture is added in a dropwise manner; the remaining amount of initiator is added by means of dropwise addition.
Optionally, the proportion of each component is optimized, and in some specific schemes, the mass ratio of methyl methacrylate, n-butyl acrylate, hydroxypropyl acrylate, methacrylic acid and styrene is 45 (16-9): 4:5:2;
the mass of the 1, 3-tetramethyl peroxy butyl-2-ethyl hexanoate is 1% -2% of that of the n-butyl acrylate;
the mass of the dodecylphenol polyoxyethylene ether is 10% -15% of the mass of the n-butyl acrylate; the mass of the allyloxy-2-hydroxy propane sodium sulfonate, allyloxy-fatty alcohol oxyvinyl ether sodium sulfonate or disodium glycolate sulfinate is 8-10% of the mass of the n-butyl acrylate.
The invention also provides a preparation method of the random crack template. The preparation method comprises spin coating the mask liquid on the surface of the optical window glass substrate to form a mask layer, and then placing the optical window coated with the mask layer in a temperature and humidity environment to generate random cracks on the surface mask layer.
Optionally, the spin-coating process conditions are optimized, and in some specific schemes, the spin-coating process conditions are that the temperature is 20-30 ℃, the humidity is 40% -45%, and the spin-coating rotating speed is 600-800 r/min.
Optionally, the temperature and humidity environment is optimized, and in some specific schemes, the humidity environment is: the temperature is set to 25-30 ℃ and the humidity is set to 40-45%.
Alternatively, the mask layer thickness is optimized, and in some embodiments, the mask layer thickness is 10-12 microns.
Alternatively, the average width of the random cracks is less than or equal to 3mm; the crack duty cycle is: 10% -20%; the average size of the grid of random cracks is: 40-100mm.
The invention also provides a preparation method of the metal mesh electromagnetic shielding optical window. The preparation of the metal mesh electromagnetic shielding optical window comprises the steps of preparing a random crack template by adopting the method, plating metal in random cracks on the surface of the random crack template, and removing the mask to prepare the metal mesh electromagnetic shielding optical window.
Alternatively, the metal is selected from Cu, ag, au, al or Ni.
The invention can solve the problems that the machining cannot be realized and the laser etching cost is high in the processing and manufacturing of the metal mesh electromagnetic shielding optical window with the random crack width of less than 3mm at present.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a random crack template.
FIG. 2 is a graph of a random crack template prepared in example 1 of the present invention.
FIG. 3 is a random crack template prepared in example 2 of the present invention.
FIG. 4 is a random crack template prepared in example 3 of the present invention.
FIG. 5 is a random crack template prepared in example 4 of the present invention.
FIG. 6 is a graph showing the transmittance of the front and rear quartz optical windows of the plated metal mesh grid prepared in example 5 of the present invention.
FIG. 7 shows the results of electromagnetic shielding performance test of quartz optical window prepared in example 5 of the present invention.
FIG. 8 is a RW-116 type random crack mask plate prepared in comparative example 1.
FIG. 9 is a RW-116 type random crack mask plate prepared in comparative example 2.
Detailed Description
Unless specifically stated otherwise, scientific and technical terms herein have been understood based on the knowledge of one of ordinary skill in the relevant art. It should be noted that, based on the present invention, those skilled in the art may perform optimization selection on the components, the mixture ratio of each component, the temperature and the duration, the order and the mode of adding the components, the mixing mode, and the like involved in the method of the present invention to achieve the effect of the present invention.
The optical window glass substrates described herein may be selected from substrates that meet the performance characteristics of the optical fiber window, such as, but not limited to, quartz glass, K9 glass, BK7 glass, fluorogallate glass, as well as silicon single crystals, germanium single crystals, zinc sulfide/selenide crystals, calcium fluoride crystals, and the like. The following examples illustrate the invention by way of example with quartz glass.
The crack average width and grid average size (i.e., the width of the grid) detection methods described in the following examples were: after the optical microscope test, crack width data (500 pieces/m) of different positions were obtained 2 ) Mesh size data (500/m) 2 ) And (5) carrying out statistics, and obtaining a corresponding average value. And the crack duty ratio is calculated after the Matlab software image recognition. The components used in the examples below are all commercially available products.
Example 1:
the monomer mixture, initiator and emulsifier used in this example were:
monomer mixture: 30.0g of Methyl Methacrylate (MMA), 10g of n-Butyl Acrylate (BA), 1.2mL of hydroxypropyl acrylate (HPA), 0.6mL of methacrylic acid (AA) and 0.6mL of phenylacetic acid (St) were mixed in a vessel by magnetic stirring to obtain a monomer mixture.
And (3) an initiator: trigonox421 was sufficiently dissolved by magnetic stirring with 0.2g of 1, 3-tetramethylperoxy-butyl-2-ethylhexanoate (Trigonox 421) and 20.0mL of ultrapure water to form an initiator.
Emulsifying agent: 0.8g of sodium allyloxy-2-hydroxypropanesulfonate (AHPS), 1.2g of dodecylphenol polyoxyethylene ether (OP-10) and 35.0mL of ultrapure water were stirred magnetically and mixed uniformly to obtain an emulsifier.
Monomer mixture, initiator and emulsifier mixture preparation:
dropwise adding the 10wt% monomer mixture into a container, adding 0.5g sodium bicarbonate to adjust the pH value to be neutral, and stirring by using a magnetic stirrer until the solution becomes a milky mixture;
heating the emulsion mixture to 75 ℃ and slowly adding a 20wt% initiator solution dropwise while stirring; after the dripping is completed, the heating temperature is raised to 80 ℃ and kept for 30min; then continuously dripping the rest 90wt% of monomer mixture and 80wt% of initiator solution, and preserving the heat for 3 hours to obtain a monomer mixture, an initiator and an emulsifier mixed solution;
and continuously heating the mixture of the monomer mixture, the initiator and the emulsifier to 85 ℃ after heat preservation, keeping the temperature for 2 hours, naturally cooling to room temperature, adding a proper amount of ammonia water to adjust the pH to be neutral, adopting a suction filtration mode, configuring a 500-mesh filter cloth with a Buchner funnel, performing suction filtration on the mixture for 3 times, and collecting filtrate to obtain mask liquid.
Further, a spin coater (KW-4T) is adopted, the rotating speed is set to be 800r/min, the mask liquid prepared by the scheme is spin-coated on clean quartz glass with an optical window, the spin coating time is 50s, and a mask layer is obtained, wherein the thickness of the mask layer is about: 9-10mm;
placing the coated optical window glass covered with the mask layer in a temperature and humidity box, wherein the temperature is set to 25 ℃, the humidity is set to 45%, and the time is controlled to 12 hours; the random cracks of the formed template are shown in figure 2, and the average width of the cracks is [ (]
) 2.6 mm, mesh average size (+.>
) The random crack mask plate with good communication of 52.3mm has the following crack duty ratio: 15%.
Example 2:
this embodiment differs from embodiment 1 in that: the monomer mixture used was: 40.0g of Methyl Methacrylate (MMA), 10g of n-Butyl Acrylate (BA), 1.6mL of hydroxypropyl acrylate (HPA), 0.8mL of methacrylic acid (AA) and 0.8mL of phenylacetic acid (St);
the random crack of the template formed in the embodiment is shown in fig. 3, the average crack width of the template is 2.2mm, the average mesh size of the template is 42.9mm, and the random crack mask template with good communication is formed, and the crack duty ratio in the embodiment is as follows: 13%.
Example 3:
this embodiment differs from embodiment 1 in that: the monomer mixture used was: 50.0g of Methyl Methacrylate (MMA), 10g of n-Butyl Acrylate (BA), 2.0mL of hydroxypropyl acrylate (HPA), 1.0mL of methacrylic acid (AA) and 1.0mL of phenylacetic acid (St); the mask layer thickness of this embodiment is about: 8-9mm;
the random crack of the template manufactured by the embodiment is shown in fig. 4, the average crack width is 1.94mm, the average mesh size is 38.5mm, the communication is good, and the crack duty ratio is: 10%.
Example 4:
this example is different from example 1 in that the template forming process is that the coated optical window glass covering the mask layer is placed in a temperature and humidity box, the temperature is set to 30 ℃, the humidity is set to 50%, and the time is controlled to 12 hours;
the formed template random crack is shown in fig. 5, the average width of the crack is 2.4mm, the average size of the grid is 51.9mm, and the random crack mask plate with good communication has the following crack duty ratio: 14%.
Further, the existing metal plating method (such as an ion source auxiliary evaporation method) can be adopted to plate metal in the random cracks on the manufactured mask plate, and after the metal plating is finished, a mask layer (or the mask plate) is removed to prepare the metal mesh grid electromagnetic shielding optical window.
Example 5:
this example uses ion source assisted vapor deposition (ion source anode voltage 200V, anode current 1.5A, argon partial pressure 3.0X10) -3 Pa, argon flow 10 sccm), and plating of random metal Cu mesh was performed by using the mask plates of example 1 (01#) and example 4 (04#), respectively, to prepare random metal Cu mesh, and to prepare metal mesh electromagnetic shielding optical window.
And then, a four-probe tester is adopted to test the square resistances of the optical windows manufactured in the embodiment, the square resistances of the samples in the embodiment 1 and the sample in the embodiment 4 are respectively 4.69 omega/sq and 3.75 omega/sq, and the connectivity of the metal lines of the grid on the surface of the sample obtained in the embodiment is good in comparison with the relevant regulations in GB/T26598-2011.
The transmittance of the sample was measured by using an ultraviolet-visible spectrophotometer, and as shown in fig. 6, the absolute transmittance of the visible light band was about 80%, and the transmittance was good in comparison with the relevant regulations in GB/T26598-2011.
Simultaneously, the electromagnetic shielding capacity of two samples of the embodiment is tested by adopting a flange coaxial method, and as shown in fig. 7, the test result shows that when the electromagnetic wave frequency is 1-3GHz, the electromagnetic shielding capacity is 44dB on average; when the electromagnetic wave frequency is 3-18GHz, the electromagnetic shielding performance is 50dB on average, and the electromagnetic shielding performance of the obtained window is excellent in comparison with relevant regulations in GB/T35575-2017.
Comparative example 1:
this comparative example is different from example 1 in that the mask liquid is replaced with: mask liquid prepared from acrylic emulsion; a commercially available acrylic emulsion (RW-116, korean Han Hua) was suction-filtered through a 500-mesh filter cloth equipped with a Buchner funnel for 3 times, and the filtrate was collected to obtain a mask liquid of this comparative example.
The random crack mask plate formed by the comparative example is shown in fig. 8, and has uneven crack width, large grid size difference and more half branch-shaped cracks, so that the overall connectivity of the template is poor.
Comparative example 2:
this comparative example is different from comparative example 1 in that the rotation speed at the time of spin coating was set to 1000r/min;
as shown in FIG. 9, the random crack mask plate formed by the comparative example has uneven crack width, large grid size difference and more half branch-shaped cracks, so that the whole communication of the mask plate is poor.
Table 1 comparison of crack template performance parameters in examples
As shown in table 1, the random crack prepared by the present invention has good line width uniformity and connectivity (i.e., the longer the crack is shared by multiple grids, the better the connectivity, and vice versa.
Claims (11)
1. The preparation method of the mask liquid is characterized by comprising the following steps: preserving heat of a mixed solution of the monomer mixture, the emulsifier and the initiator at 80-85 ℃, cooling, adjusting the pH value to be neutral after cooling to room temperature, filtering with 400-500 mesh filter cloth or a filter membrane, and collecting filtrate as mask liquid;
the monomer mixture is a mixture of methyl methacrylate, n-butyl acrylate, hydroxypropyl acrylate, methacrylic acid and styrene;
the emulsifier is an aqueous solution of allyloxy-2-hydroxy propane sodium sulfonate and dodecylphenol polyoxyethylene ether, or an aqueous solution of allyloxy-fatty alcohol oxyvinyl ether sodium sulfonate and dodecylphenol polyoxyethylene ether, or an aqueous solution of disodium glycolate and dodecylphenol polyoxyethylene ether;
the initiator is an aqueous solution of 1, 3-tetramethyl peroxy-butyl-2-ethylhexanoate.
2. The mask liquid according to claim 1, wherein the method for preparing the mixed liquid of the monomer mixture, the emulsifier and the initiator comprises: mixing the emulsifier and a part of the monomer mixture, regulating the pH value to be neutral, uniformly mixing, heating to 70-75 ℃, adding a part of the initiator, continuously heating to 75-80 ℃, preserving heat, adding the rest of the monomer mixture and the rest of the initiator, mixing, and preserving heat.
3. The mask liquid according to claim 2, wherein the partial amount of the initiator is added by dropwise addition; the rest amount of the monomer mixture is added in a dropwise manner; the remaining amount of initiator is added by means of dropwise addition.
4. The mask liquid according to claim 1, wherein the mass ratio of methyl methacrylate, n-butyl acrylate, hydroxypropyl acrylate, methacrylic acid and styrene is 45 (16-9): 4:5:2;
the mass of the 1, 3-tetramethyl peroxy butyl-2-ethyl hexanoate is 1% -2% of that of the n-butyl acrylate;
the mass of the dodecylphenol polyoxyethylene ether is 10% -15% of the mass of the n-butyl acrylate; the mass of the allyloxy-2-hydroxy propane sodium sulfonate, allyloxy-fatty alcohol oxyvinyl ether sodium sulfonate or disodium glycolate sulfinate is 8-10% of the mass of the n-butyl acrylate.
5. A preparation method of a random crack template is characterized in that the method comprises the steps of spin-coating the mask liquid according to any one of claims 1-4 on the surface of an optical window glass substrate to form a mask layer, and then placing the optical window coated with the mask layer in a temperature and humidity environment to generate random cracks on the surface mask layer.
6. The method for preparing a random crack template according to claim 5, wherein the spin-coating process condition is that the temperature is 20-30 ℃, the humidity is 40% -45%, and the spin-coating rotating speed is 600-800 r/min.
7. The method for preparing a random crack template according to claim 5, wherein the temperature and humidity environment is: the temperature is set to 25-30 ℃ and the humidity is set to 40-45%.
8. The method of claim 5, wherein the mask layer has a thickness of 10 to 12 microns.
9. The method of producing a random crack template according to claim 5, wherein the average width of the random crack is 3mm or less; the crack duty cycle is: 10% -20%; the average size of the grid of random cracks is: 40-100mm.
10. A method for preparing a metal mesh electromagnetic shielding optical window, which is characterized in that a random crack template is prepared by adopting the method of any one of claims 5-9, then metal is plated in random cracks on the surface of the random crack template, and then a mask is removed to prepare the metal mesh electromagnetic shielding optical window.
11. The method of manufacturing a metal mesh electromagnetic shielding optical window according to claim 10, wherein the metal is selected from Cu, ag, au, al or Ni.
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