CN105152546B - A kind of transparent nonpolluting coating material for glass, transparent nonpolluting coating and preparation method thereof - Google Patents
A kind of transparent nonpolluting coating material for glass, transparent nonpolluting coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of transparent nonpolluting coating material for glass, transparent nonpolluting coating and preparation method thereof, the material includes aerosil nano-particle, the mixed dispersion liquid of low-surface-energy binding agent and solvent composition.The invention also discloses the preparation method of the transparent nonpolluting coating, is coated to substrate of glass by the mixed dispersion liquid of aerosil nanoparticle dispersion liquid and low-surface-energy binding agent and prepares the coating with micro-nano structure, cold curing.Hydrophobic coating material provided by the invention and preparation method thereof is few to Material Needs, and advantages of nontoxic raw materials, use cost is low, and method is simple, and it is convenient to apply, and can carry out the preparation of large-area transparent nonpolluting coating；The coating being prepared has excellent hydrophobicity, the transparency, soil resistance and can erasing property repeatedly.
Description
Technical field
The present invention relates to the technical field of nonpolluting coating material, and in particular to a kind of to have optical transparence concurrently simultaneously, prevent
Only surface is contaminated, the renewable coating for glass surface.
Background technology
The various aspects that glass be used to produce and live, it is desirable to keep its clean, transparent.Daily life
In, the pollutant of glass is mainly water droplet, mud drop, coffee etc., and hydrophobic surface has the characteristics that waterproof, automatically cleaning, therefore is ground
The surface that fixture has hydrophobic antifouling property causes scientist widely concern and attention.Two need to typically be met by preparing hydrophobic surface
Individual key factor：First, surface has the structure of micro-scale, when water droplet contacts with surface can not complete wetting surface, air quilt
Micro-structured inner is retained in so as to form air bag, due to the presence of air bag, water droplet can slip away from surface easily；Second,
Material has the material of low-surface-energy or the layered low-surface energy of surface attachment one in itself.
It is typically a variety of by template, photoetch method, plasma etching method, layer assembly method etc. to prepare super hydrophobic surface
Technology and method.These methods cause it to be only applicable to the super thin of laboratory research or small area due to the requirement height to equipment
It is prepared by water surface.
The super-hydrophobic coat developed based on coating technology can reduce the demand to equipment, while simplify construction procedure,
Possibility is brought for the fast and effective hydrophobic surface for preparing of large area.Chinese patent application CN103964701A discloses a kind of titanium dioxide
The preparation method of silicon/polytetrafluoroethylene (PTFE) hydridization super-hydrophobic coat, by silane coupler at appropriate temperature and pH value condition
Hydrolyze in alcohol water mixed solvent and reacted with Ludox, make silica particle surface grafting organic group；After modification
The ptfe emulsion of certain volume is added in Ludox and auxiliary agent is made homogeneous mixture system and is aged certain time, then
It prepares coating, both can effectively improve the bonding force of polytetrafluoroethylene (PTFE) and base material, improve hardness and wearability, again can structure coating
The roughness on surface, so as to improve the contact angle on surface.
It is worthy of note that optical demands high (such as windshield, building window glass, swimming goggle eyepiece etc.)
When carrying out coating, then in addition to hydrophobic, it is little also to require that coating influences on the translucency of glass.Chinese patent CN 102051120
A disclose a kind of mechanical strength is higher, durability preferably, prepare simple super-hydrophobic coat preparation method.By spraying technology,
Mixed dispersion liquid in composite nano inoganic particle, polysiloxane compound, water and emulsifying agent or organic solvent is sprayed into base
Basal surface, super hydrophobic surface is prepared in high-temperature heat treatment, but this method needs particular device-spray gun to use, and coating is not
It is transparent.
Chinese patent application CN104046152A discloses a kind of preparation method of polystyrene super-hydrophobic coat, by polyphenyl
Ethene nano particle is dispersed, and then baking melts polystyrene nanoparticles under high temperature (160~230 DEG C), takes out
Naturally dry, the slightly aobvious complexity of this method construction.
Chinese patent application CN103788802A discloses a kind of preparation method of fluorine-containing super-hydrophobic coat, prepares fluorine first
Modified polyacrylate, it is dissolved in organic solvent, adds silane coupler modified nano-silicon dioxide particle, obtains compound molten
Glue；The complex sol described in application on base material, solidify drying.There is good hydrophobic performance after the super-hydrophobic coat solidification of preparation
And mechanical property, while there is preferable heat resistance, but the transparency of coating is not referred to.
The content of the invention
The technical problems to be solved by the invention be overcome existing hydrophobic nonpolluting coating preparation method more using toxic reagent,
Process is numerous and diverse, and the problem of can not obtain the transparency simultaneously, there is provided a kind of transparent nonpolluting coating material for glass, transparent
Nonpolluting coating and preparation method thereof.
A kind of transparent nonpolluting coating material for glass surface, by aerosil nanoparticle dispersion liquid and low table
Face energy binding agent is made；
Wherein, described aerosil nanoparticle dispersion liquid is scattered in solvent by aerosil nano-particle
Middle formation；
The specific surface area of described aerosil nano-particle is 50m2/ g~800m2/ g, mass percent concentration are
0.1%~50%.
Using the coating that is formed in glass surface of material of the present invention, not only with preferable anti-fouling effect, and also it is transparent
Property it is fine, and the material can form coating by the method for brushing in glass surface, simple to operate.
The specific surface area of described aerosil nano-particle is excessive or too small all bad, when specific surface area is too small
When, the antifouling property of coating that can cause to obtain declines, and when specific surface area is excessive, transparent performance reduces again, preferably, institute
The specific surface area for the aerosil nano-particle stated is preferably 100~600m2/ g, most preferably 300m2/g。
Concentration of the described aerosil nano-particle in dispersion liquid can produce large effect to transparent performance,
If concentration is excessive, transparent performance can be caused to reduce, preferably, the weight percent of described aerosil nano-particle
Than being preferably 1%~25%.
Described low-surface-energy binding agent can fix the porous microstructure formed by Nano particles of silicon dioxide, while
Adhesion is provided between coating and substrate.Preferably, the low-surface-energy binding agent be hexadecyl trimethoxy silane,
3- aminopropyl triethoxysilanes, MTES, vinyltrimethoxy silane, phenyltrimethoxysila,e, third
Ethyl triethoxy silicane alkane or dimethyldimethoxysil,ne, its dosage for the aerosil mass particle 10%~
200%.The species of described low-surface-energy binding agent can produce large effect to antifouling property, as it is further preferably,
The described low-surface-energy binding agent is MTES, hexadecyl trimethoxy silane, phenyl trimethoxy
During silane, it can cause coating that there is higher contact angle and lower roll angle, also imply that the antifouling property of coating more
It is good.
Described solvent is low boiling alcohols.Described alcohols solvent is following one or more：It is ethanol, methanol, different
Propyl alcohol etc..For the consideration to health, nontoxic or less toxic ethanol, isopropanol are typically chosen.
Present invention also offers a kind of transparent nonpolluting coating, is prepared by described nonpolluting coating material.
Present invention also offers a kind of preparation method of described transparent nonpolluting coating, comprise the following steps：
(1) aerosil nano-particle is disperseed to the nanoparticle dispersion liquid stablized in a solvent；
(2) low-surface-energy binding agent is added in the nanoparticle dispersion liquid that step (1) obtains and obtains mixed dispersion liquid, so
Afterwards plus acid for adjusting pH value is to 4~5；
(3) step (2) is obtained into mixed dispersion liquid to be added drop-wise on cloth, cloth is mixed dispersion liquid wetting completely；
(4) with the cloth cleaning glass window surface after being wet, then make after solvent volatilizees completely, to be solidified to obtain institute
The transparent nonpolluting coating stated.
Preferably, in step (2), described acid is hydrochloric acid, concentration 1mol/L.
Preferably, in step (3), the material of described cloth is woven dacron, cotton or non-woven fabrics.
Preferably, in step (4), solidification temperature is room temperature, and hardening time is 1~24h.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) raw material used in transparent nonpolluting coating preparation process of the invention are green material, to ring
Border is pollution-free, harmless to human body.
(2) transparent nonpolluting coating of the invention possesses the very outstanding transparency, the translucency of glass is influenceed little.
(3) for transparent nonpolluting coating of the invention for the aqueous dispersion of complexity, such as coffee, sludge show stabilization
Anti-wettability, possesses certain self-cleaning function.
(4) preparation method of transparent nonpolluting coating material and coating of the invention is simple and convenient, is obtained using ultrasonic disperse
To the dispersion liquid of aerosil nano-particle, by rag wipe method by aerosil nano-particle and low-surface-energy
Binding agent mixed dispersion liquid is relatively evenly coated on substrate surface, and subsequent solvent quickly volatilizees, and cold curing can obtain surface
Porous microstructure, the processing such as high temperature, high pressure, freezing is not required to, also without the use of special equipment, is easy to commercial introduction and day
Often application.When not needing anti-pollution function or after coating destroyed by accidentalia, the methods of scouring can be passed through quick erasing without
Damage the surface nature of substrate of glass.It when needing transparent anti-pollution function again, can quickly be rubbed, be had renewable again
Property.
Brief description of the drawings
Fig. 1 is the contact angle test chart of nonpolluting coating made from the embodiment of the present invention 1 and water droplet；
Fig. 2 is nonpolluting coating transparency photo made from the embodiment of the present invention 1；
Fig. 3 is super-hydrophobic coat self-cleaning function demonstration graph made from the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscopic picture of nonpolluting coating made from the embodiment of the present invention 1；
Fig. 5 is that super-hydrophobic coat preparation method described in the embodiment of the present invention 1 carries out coating-cleaning repeatedly to same glass
Contact angular data.
Embodiment
Unless otherwise specified, the various raw materials in the present invention are commercially available prod；Or can be according to generally in the art
Preparation method obtains.Unless otherwise indicated or explanation, technical term used herein are identical with this area routine term.
Embodiment 1
(1) commercially available aerosil nano-particle (the specific surface area 300m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 0.5g MTESs are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
(3) the terylene rag cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Wiped with the textile cloth
Glass surface is wiped, transparent nonpolluting coating can be formed after then glass is placed at room temperature 3 hours.
Contact angle tester is used to measure the transparent nonpolluting coating to the contact angle of water droplet as 146.5 ° (Fig. 1), roll angle
About 25 °.Fig. 2 shows that the nonpolluting coating possesses the outstanding transparency, and when wavelength is about 550nm, light transmittance is about 90.3% (nothing
91.8%) light transmittance of coated glass is about.Fig. 3 shows that the nonpolluting coating has automatical cleaning ability, wherein, left figure is several to be added dropwise
The picture after sewage is dripped, right figure is to drip off the picture after sewage after tilting low-angle.Coating can be found using scanning electron microscopic observation
With porous microstructure (Fig. 4).
Super-hydrophobic coat is first prepared according to the method in embodiment 1, contact angle and roll angle are measured, then with commercially available
Glass cleaner coating cleaning after glass, measure contact angle, above-mentioned steps repeated, investigate the side of use of the invention
The repeatability of method, is shown in Fig. 5.It can be seen that method of the invention is a kind of gentle method, substrate will not be caused to damage, can be with
Coating repeatedly is carried out to substrate surface using the method for the present invention, and easily can be removed coating when not needed.
Embodiment 2
(1) commercially available aerosil nano-particle (the specific surface area 300m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 0.5g hexadecyl trimethoxy silanes are added into above-mentioned dispersion liquid, it is 1mol/L's that a few drop concentration, which are added dropwise,
The pH value of hydrochloric acid regulation mixed dispersion liquid is between 4~5.
(3) the terylene rag cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Wiped with the textile cloth
Glass surface is wiped, transparent nonpolluting coating is can obtain after then glass is placed at room temperature 3 hours.
The transparent nonpolluting coating contact angle is 135.0 °, and roll angle is 30 °.Other performances such as the transparency, automatical cleaning ability
Etc. same as Example 1.
Embodiment 3
(1) commercially available aerosil nano-particle (the specific surface area 100m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 0.5g MTESs are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
(3) the terylene rag cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Wiped with the textile cloth
Glass surface is wiped, transparent nonpolluting coating is can obtain after then glass is placed at room temperature 2 hours.
The transparent nonpolluting coating contact angle is 135.0 °, and roll angle is 30 °.Other performances such as the transparency, automatical cleaning ability
Etc. similar to Example 1.
Embodiment 4
(1) commercially available aerosil nano-particle (the specific surface area 600m of 0.5g are weighed respectively2/ g) and 50g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 0.5g MTESs are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
(3) the terylene rag cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Wiped with the textile cloth
Glass surface is wiped, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 1 hour.
The transparent nonpolluting coating contact angle is 140.0 °, and roll angle is about 30 °.The transparency is more excellent compared with embodiment 1, and wavelength is about
For 550nm when, light transmittance is about 90.8%.
Embodiment 5
(1) commercially available aerosil nano-particle (the specific surface area 600m of 3.0g are weighed respectively2/ g) and 10g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 1.5g MTESs are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
(3) the terylene rag cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Wiped with the textile cloth
Glass surface is wiped, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 20 hours.
The transparent nonpolluting coating contact angle is 139.2 °, and roll angle is 25 °.The transparency is slightly worse compared with embodiment 1, and wavelength is about
During 550nm, light transmittance is about 84.2%.
Embodiment 6
(1) commercially available aerosil nano-particle (the specific surface area 300m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 2.0g MTESs are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
(3) the nylon rag cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Wiped with the textile cloth
Glass surface is wiped, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 5 hours.
The transparent nonpolluting coating contact angle is 113.0 °, and roll angle is 38 °.The transparency is poor compared with embodiment 1.Wavelength is about
During 550nm, light transmittance is about 84.6%.
Embodiment 7
(1) commercially available aerosil nano-particle (the specific surface area 800m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
(2) 0.5g 3- aminopropyl triethoxysilanes are added into above-mentioned dispersion liquid, it is 1mol/L's that a few drop concentration, which are added dropwise,
The pH value of hydrochloric acid regulation mixed dispersion liquid is between 4~5.
(3) the cotton cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Glass is wiped with the textile cloth
Glass surface, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 5 hours.
The transparent nonpolluting coating contact angle is 100.1 °, and roll angle is 60 °.The transparency is poor compared with embodiment 1.Wavelength is about
During 550nm, light transmittance is about 83.1%.
Embodiment 8
(1) commercially available aerosil nano-particle (the specific surface area 800m of 1.0g are weighed respectively2/ g) and 20g isopropyls
Alcohol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in isopropanol by ultrasonic disperse instrument.
(2) 0.5g MTESs are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
(3) the cotton cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Glass is wiped with the textile cloth
Glass surface, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 5 hours.
The transparent nonpolluting coating contact angle is 136.0 °, and roll angle is about 37 °.The transparency is slightly worse compared with embodiment 1.Wavelength is about
For 550nm when, light transmittance is about 86.2%.
Embodiment 9
1st, commercially available aerosil nano-particle (the specific surface area 800m of 1.0g are weighed respectively2/ g) and 20g methanol,
Aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in methanol by ultrasonic disperse instrument.
2nd, 0.5g vinyltrimethoxy silanes are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
3rd, the cotton cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Glass is wiped with the textile cloth
Glass surface, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 10 hours.
The transparent nonpolluting coating contact angle is 126.0 °, and roll angle is 40 °.The transparency is slightly worse compared with embodiment 1.Wavelength is about
During 550nm, light transmittance is about 86.7%.
Embodiment 10
1st, commercially available aerosil nano-particle (the specific surface area 800m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
2nd, 0.5g dimethyldiethoxysilanes are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise
The pH value of mixed dispersion liquid is adjusted between 4~5.
3rd, the cotton cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Glass is wiped with the textile cloth
Glass surface, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 5 hours.
The transparent nonpolluting coating contact angle is 105.0 °, and roll angle is about 50 °.The transparency it is poor compared with embodiment 1, film it is uniform
Property is also poor.When wavelength is about 550nm, light transmittance is about 82.3%.
Embodiment 11
1st, commercially available aerosil nano-particle (the specific surface area 300m of 1.0g are weighed respectively2/ g) and 20g it is anhydrous
Ethanol, aerosil nano-particle is scattered in the dispersion liquid that stable homogeneous is obtained in ethanol by ultrasonic disperse instrument.
2nd, 0.5g phenyl triethoxysilanes are added into above-mentioned dispersion liquid, the hydrochloric acid that a few drop concentration are 1mol/L is added dropwise and adjusts
The pH value of mixed dispersion liquid is saved between 4~5.
3rd, the nylon cloth of certain size is intercepted, infiltrates the cloth with above-mentioned mixed dispersion liquid.Glass is wiped with the textile cloth
Glass surface, transparent hydrophobic coating is can obtain after then glass is placed at room temperature 5 hours.
The transparent nonpolluting coating contact angle is 142.0 °, and roll angle is 35 °.The transparency is close with embodiment 1.
Claims (3)
1. a kind of preparation method of transparent nonpolluting coating, it is characterised in that comprise the following steps：
(1) aerosil nano-particle is disperseed to the nanoparticle dispersion liquid stablized in a solvent；
(2) low-surface-energy binding agent is added in the nanoparticle dispersion liquid that step (1) obtains and obtains mixed dispersion liquid, Ran Houjia
Acid for adjusting pH value is to 4~5；
(3) step (2) is obtained into mixed dispersion liquid to be added drop-wise on cloth, cloth is mixed dispersion liquid wetting completely；
(4) with the cloth cleaning glass window surface after being wet, then make after solvent volatilizees completely, solidified to obtain described
Transparent nonpolluting coating；Solidification temperature is room temperature, and hardening time is 1~24h；
The specific surface area of described aerosil nano-particle is 50m2/ g~800m2/ g, mass percent concentration are
0.1%~50%；
The low-surface-energy binding agent is hexadecyl trimethoxy silane, 3- aminopropyl triethoxysilanes, the ethoxy of methyl three
Base silane, vinyltrimethoxy silane, phenyltrimethoxysila,e, propyl-triethoxysilicane or dimethylformamide dimethyl epoxide silicon
Alkane, its dosage are the 10%~200% of the aerosil mass particle；
Described solvent is at least one of ethanol, methanol and isopropanol.
2. the preparation method of transparent nonpolluting coating according to claim 1, it is characterised in that in step (2), described acid
For hydrochloric acid, concentration 1mol/L.
3. the preparation method of transparent nonpolluting coating according to claim 1, it is characterised in that in step (3), described cloth
The material of bar is woven dacron, cotton or non-woven fabrics.
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| CN105461237B (en) * | 2015-12-28 | 2018-05-29 | 太仓耀华玻璃有限公司 | A kind of LOW-E Low emissivities vacuum insulating glass and its production method |
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| CN105440751A (en) * | 2015-12-28 | 2016-03-30 | 太仓耀华玻璃有限公司 | Thermal insulation coating for curtain-wall glass and production method of thermal insulation coating |
| CN110272644A (en) * | 2018-03-14 | 2019-09-24 | 苏州鼎奕通材料科技有限公司 | The antifouling preposition primary coat liquid of oleophobic and the antifouling setting method of kitchen tools oleophobic |
| CN111440468B (en) * | 2019-01-17 | 2021-11-30 | 天津理工大学 | Nano super-hydrophobic coating additive and preparation method and application thereof |
| CN111041838B (en) * | 2019-12-27 | 2022-06-28 | 苏州东杏表面技术有限公司 | Wet tissue and preparation method and application thereof |
| CN115430916B (en) * | 2022-09-16 | 2023-05-23 | 中山大学 | Method and system for preparing micro-nano structure by laser based on matching layer |
| CN115403967A (en) * | 2022-09-29 | 2022-11-29 | 广东电网有限责任公司 | Anti-condensation flashover coating and construction process thereof |
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| CN104449357A (en) * | 2014-11-26 | 2015-03-25 | 浙江大学 | Transparent super-hydrophobic coating material and method for preparing transparent super-hydrophobic coating by transparent super-hydrophobic coating material |
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| CN104449357A (en) * | 2014-11-26 | 2015-03-25 | 浙江大学 | Transparent super-hydrophobic coating material and method for preparing transparent super-hydrophobic coating by transparent super-hydrophobic coating material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105461237B (en) * | 2015-12-28 | 2018-05-29 | 太仓耀华玻璃有限公司 | A kind of LOW-E Low emissivities vacuum insulating glass and its production method |
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