CN102501477B - Super-hydrophobic glass and manufacturing method thereof - Google Patents
Super-hydrophobic glass and manufacturing method thereof Download PDFInfo
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- CN102501477B CN102501477B CN201110306902.4A CN201110306902A CN102501477B CN 102501477 B CN102501477 B CN 102501477B CN 201110306902 A CN201110306902 A CN 201110306902A CN 102501477 B CN102501477 B CN 102501477B
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- 239000011521 glass Substances 0.000 title claims abstract description 100
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 99
- 239000011347 resin Substances 0.000 claims abstract description 99
- 239000002086 nanomaterial Substances 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 107
- 239000000243 solution Substances 0.000 claims description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 70
- 239000008187 granular material Substances 0.000 claims description 63
- 239000003513 alkali Substances 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 40
- 230000002209 hydrophobic effect Effects 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000004519 grease Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 229920001296 polysiloxane Polymers 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000012895 dilution Substances 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- -1 amide groups amine Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- GZBAUYZREARCNR-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OC)(OC)OC.[F] Chemical class C(CCCCCCCCC)[Si](OC)(OC)OC.[F] GZBAUYZREARCNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 22
- 239000010408 film Substances 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 229960000583 acetic acid Drugs 0.000 description 11
- 239000012362 glacial acetic acid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000003607 modifier Substances 0.000 description 7
- 239000004575 stone Substances 0.000 description 7
- 238000001338 self-assembly Methods 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000005348 self-cleaning glass Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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Abstract
The invention provides super-hydrophobic glass and a manufacturing method thereof; the super-hydrophobic glass comprises a glass substrate and a micro-nano structure layer disposed on the glass surface; a resin layer is disposed between the glass substrate and the micro-nano structure layer to increase the bonding force between the micro-nano structure layer and the glass substrate. The super-hydrophobic glass not only has excellent hydrophobicity, but also can maintain the hydrophobicity for a long time, which promotes the industrialization of the super-hydrophobic glass.
Description
Technical field
The present invention relates to a kind of super-hydrophobic glass and preparation method thereof.
Background technology
Universal and the skyscraper of automobile increase the favor making the glass with self-cleaning function obtain market.Typical self-cleaning glass utilizes self-cleaning material to make a self-cleaning film at glass surface, prevents contamination by dust, sleet is bonded in glass surface by self-cleaning film, microorganism adhering can also be suppressed at glass surface simultaneously.
Common self-cleaning film comprises hydrophilic film and hydrophobic film.Wherein, hydrophilic film requires to be less than 10 ° with the contact angle of water, the hydroxyl that the photocatalysis that its hydrophilicity stems from film generates.When preparing hydrophilic film, need to carry out high-temperature baking technique.Hydrophobic film requires to be greater than 90 ° with the contact angle of water, and its hydrophobic performance stems from the film of micro nano structure and low-surface-energy, and the film of micro-nano structure can form larger air entrapment rate, and low-surface-energy can reduce the adhesiveness of film and water droplet.
Compared with hydrophilic film, hydrophobic film has the following advantages: the first, can obtain hydrophobic film at normal temperatures and pressures, thus can avoid the adverse effect that high-temperature baking may cause glass basis; The second, resistance to soiling is given prominence to, and its hydrophobicity can avoid glass and strong acid, highly basic, reductant-oxidant etc. to corrode solvent contacts as far as possible, thus can reduce the destruction that deep-etching solution may cause glass.Therefore, the self-cleaning glass application prospect with hydrophobic function is extensive.
But the wearability of existing hydrophobic film is poor, the as easy as rolling off a log hydrophobicity of self-cleaning glass that causes of the wearing and tearing in use procedure reduces, and this makes hydrophobic self-cleaning glass never have industrialization.In addition, the surface roughness of film is restriction mutually on the transparency of film and hydrophobic impact.The increase of surface roughness must increase the scattering of light in film in communication process.Therefore, on the one hand, thin-film hydrophobic strengthens due to the increase of surface roughness; On the other hand, the transparency of film but reduces with the increase of roughness.
Summary of the invention
The present invention proposes a kind of super-hydrophobic glass and preparation method thereof, this super-hydrophobic glass has good wearability, thus super-hydrophobic glass can be made to keep its hydrophobicity for a long time.
In order to achieve the above object, the present invention proposes a kind of super-hydrophobic glass, comprise substrate of glass and be arranged on the micro nano structure layer of described glass surface, resin bed is provided with, to improve the adhesion between described micro nano structure layer and described substrate of glass between described substrate of glass and described micro nano structure layer.
Preferably, the material component of described resin bed comprise percentage by weight be 60 ~ 95 transparent resin, percentage by weight be 1 ~ 30 curing agent and percentage by weight be the coupling agent of 0.05 ~ 2.
Preferably, described transparent resin is epoxy resin, unsaturated-resin or phenolic resins.
Preferably, described curing agent be aliphatic amine, aromatic amines, amide groups amine, solidification amine or urea substitute of hiding.
Preferably, described coupling agent is KH-550, KH-560, KH-570, KH792, DL602, DL171, A-151.
Preferably, the thickness of described resin bed is 10 ~ 1000nm.
Preferably, described micro nano structure layer is the silica agglomerates of sub-micron-nanostructured, and the particle diameter of described silica agglomerates is not more than 400nm.
Preferably, be also provided with hydrophobic decorative layer on the surface of described micro nano structure layer, described hydrophobic decorative layer adopts trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane or perfluoroalkyl alkoxy silane to make.
The present invention also provides a kind of preparation method of super-hydrophobic glass, comprises the following steps: make resin solution; Described resin solution is coated in glass basic surface and forms resin bed; Micro nano structure layer is made on the surface of described resin bed; Described resin bed is solidified, makes described micro nano structure layer and described glass bond together simultaneously.
Preferably, described resin solution obtains in the following manner: namely, the curing agent of the transparent resin of 60 ~ 95 weight portions, 1 ~ 30 weight portion, the coupling agent of 0.05 ~ 2 weight portion added in the solvent of 100 ~ 1000 weight portions and mix.
Preferably, described transparent resin adopts the one in epoxy resin, unsaturated-resin or phenolic resins.
Preferably, described curing agent employing aliphatic amine, aromatic amines, amide groups amine, the one of solidifying in amine or urea substitute of hiding.
Preferably, described coupling agent adopts KH-550, KH-560, KH-570, KH792, the one in DL602, DL171, A-151.
Preferably, the thickness of the described resin bed applied at described glass basic surface is 10 ~ 1000nm, and thickness difference is less than 500nm.
Preferably, the step making micro nano structure layer on the surface of described resin bed comprises: formed by silicone grease hydrolysis and comprise the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm, and include the second colloidal sol that particle diameter is the silica dioxide granule of 200 ~ 400nm; In described first colloidal sol and the second colloidal sol, add coupling agent respectively, mutually bond to make the silica dioxide granule in described first colloidal sol and the second colloidal sol; The pH value of described first colloidal sol and the second colloidal sol is regulated to be 2 ~ 4; By described first colloidal sol and the mixing of the second colloidal sol, obtain the aggregate of sub-micron-nanostructured; Described aggregate is coated in the surface of described resin bed.
Preferably, be hydrolyzed by described silicone grease and obtain that to include particle diameter be that the step of described first colloidal sol of the silica dioxide granule of 10 ~ 100nm comprises: alkali lye and organic solvent are mixed, and stir at the temperature of 20 ~ 80 DEG C and obtain solution; With organic solvent by adding in described solution after the dilution of described silicone grease, make the temperature of described solution remain on 20 ~ 80 DEG C, the mol ratio of the alkali in described silicone grease and described alkali lye is: 0.5 ~ 3 simultaneously; Stir described solution 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm.
Preferably, be hydrolyzed by described silicone grease and obtain that to include particle diameter be that the step of described second colloidal sol of the silica dioxide granule of 200 ~ 400nm comprises: alkali lye and organic solvent are mixed, and stir at the temperature of 20 ~ 80 DEG C and obtain solution; With organic solvent by adding in described solution after the dilution of described silicone grease, temperature is remained on 20 ~ 80 DEG C, the mol ratio of the alkali in described silicone grease and described alkali lye is: 0.5 ~ 3 simultaneously; Stir described solution 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm; Alkali lye, the first colloidal sol and organic solvent are mixed into C solution at the temperature of 20 ~ 80 DEG C; To add in described C solution after described silicone grease dilution with organic solvent, described solution is stirred 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, to make described silica dioxide granule grow up, thus acquisition includes described second colloidal sol that particle diameter is the silica dioxide granule of 200 ~ 400nm.
Preferably, described silicone grease is ethyl orthosilicate or butyl silicate.
Preferably, described alkali lye is ammoniacal liquor, NaOH or potassium hydroxide.
Preferably, described organic solvent is ethanol, methyl alcohol or acetone.
Preferably, described resin bed is that insulation solidify to form resin bed in 30 ~ 450 minutes at the temperature of 20 ~ 180 DEG C.
Preferably, the thickness of described micro nano structure layer is less than or equal to 600nm.
Compared with prior art, the present invention has following beneficial effect:
Super-hydrophobic glass provided by the invention arranges resin bed between substrate of glass and micro nano structure layer, resin bed can improve the adhesion of micro nano structure layer and substrate of glass, thus improve the wearability of micro nano structure layer, thus super-hydrophobic glass is enable to keep its hydrophobicity for a long time.Therefore, this super-hydrophobic glass not only has excellent hydrophobicity, and can keep its hydrophobicity for a long time, thus super-hydrophobic glass is strided forward to industrialization.
As a preferred embodiment of the present invention, the size of the micro nano structure layer in super-hydrophobic glass is not more than the wavelength of visible ray, namely 400nm is less than or equal to, this can reduce visible ray through scattered power during micro nano structure layer, thus make the surface roughness of micro nano structure layer and visible light transmittance rate obtain good balance, and then making the contact angle of super-hydrophobic glass be greater than 150 °, roll angle is less than 10 °, and the light transmittance of visible ray can reach more than 85%.
Similarly, the preparation method of super-hydrophobic glass provided by the invention first makes resin bed on the glass substrate, then " plantation " micro nano structure layer on the resin layer, the adhesion of micro nano structure layer and substrate of glass can be improved by resin bed, thus improve the wearability of micro nano structure layer, and then super-hydrophobic glass is enable to keep its hydrophobic performance for a long time.Therefore, this super-hydrophobic glass not only has excellent hydrophobicity and wearability, and can keep its hydrophobicity for a long time, thus super-hydrophobic glass is strided forward to industrialization.
As a preferred embodiment of the present invention, by the preparation method of silica dioxide granule provided by the invention, prepare sub-micron-nanostructured, the silica dioxide granule of reunion shape, and make the particle diameter of silica dioxide granule be less than 400nm, thus the scattering that can reduce when light is propagated in micro nano structure layer, and then improve the transparency of super-hydrophobic glass.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the sectional view of super-hydrophobic glass provided by the invention, and
Fig. 2 is the flow chart of super-hydrophobic glass preparation method provided by the invention.
Detailed description of the invention
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, super-hydrophobic glass that the present invention proposes and preparation method thereof is described in detail.
Fig. 1 is the sectional view of super-hydrophobic glass provided by the invention.Refer to Fig. 1, the super-hydrophobic glass that the present embodiment provides comprises substrate of glass 1, resin bed 2, micro-nano structure layer 3 and hydrophobic decorative layer 4, and resin bed 2, micro-nano structure layer 3 and hydrophobic decorative layer 4 are stacked in substrate of glass 1 surface successively from substrate of glass 1.
The thickness of resin bed 2 is 10 ~ 1000nm, preferably 100 ~ 400nm.The material component of resin bed 2 comprise percentage by weight be 60 ~ 95 transparent resin, percentage by weight be 1 ~ 30 curing agent and percentage by weight be the coupling agent of 0.05 ~ 2.Wherein,
Transparent resin can adopt epoxy resin, unsaturated-resin or phenolic resins.Curing agent can adopt aliphatic amine, aromatic amines, amide groups amine, hide solidification amine or urea substitute.Coupling agent can adopt KH-550, KH-560, KH-570, KH792, DL602, DL171 or A-151.
Micro nano structure layer 3 is silica micro nano structure layer, and, the size of silica micro nano structure is not more than visible wavelength, namely 400nm is less than or equal to, this can reduce visible ray through scattered power during micro nano structure layer 3, thus makes the surface roughness of micro nano structure layer 3 and visible light transmittance rate obtain good balance, and then makes the contact angle of super-hydrophobic glass be greater than 150 °, roll angle is less than 10 °, and the light transmittance of visible ray can reach more than 85%.The thickness of micro nano structure layer 3 is no more than 600nm, preferably 400 ~ 500nm.
Hydrophobic decorative layer 4 adopts trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane or perfluoroalkyl alkoxy silane material to make.
The super-hydrophobic glass that the present embodiment provides arranges resin bed between substrate of glass and micro nano structure layer, to improve the wearability of micro nano structure layer, thus enables super-hydrophobic glass keep its hydrophobicity for a long time.Therefore, this super-hydrophobic glass not only has excellent hydrophobicity and wearability, and can keep its hydrophobicity for a long time, thus super-hydrophobic glass is strided forward to industrialization.
The present embodiment also provides a kind of preparation method of super-hydrophobic glass.Fig. 2 is the flow chart of super-hydrophobic glass preparation method provided by the invention.Refer to Fig. 2, the preparation method of super-hydrophobic glass comprises the following steps:
Step s10, makes resin solution.
Resin solution the curing agent of the transparent resin of 60 ~ 95 weight portions, 1 ~ 30 weight portion, the coupling agent of 0.05 ~ 2 weight portion is added in the solvent of 100 ~ 1000 weight portions to mix.Wherein, transparent resin adopts the one in epoxy resin, unsaturated-resin or phenolic resins.The one that curing agent adopts aliphatic amine, aromatic amines, amide groups amine, hides in solidification amine or urea substitute.Coupling agent adopts KH-550, KH-560, KH-570, KH792, the one in DL602, DL171, A-151.Solvent adopts the one in dimethyl formamide, three oxygen ethene, ethylene glycol phenyl ether, dimethylbenzene.
Step s20, is coated in the surface of substrate of glass to form resin bed by resin solution.
Adopt manual blade coating, mechanical blade coating, high-frequency screen to tremble the existing techniques such as coating, the resin solution made is coated in the surface of substrate of glass to form resin bed by step s10.Be 10 ~ 1000nm at the thickness of resin bed of glass basic surface coating, and thickness difference is less than 500nm.
Step s30, makes micro nano structure layer on the surface of resin bed.
The manufacturing process of micro nano structure layer comprises the following steps:
Step s31, is formed by silicone grease hydrolysis and comprises the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm, and include the second colloidal sol that particle diameter is the silica dioxide granule of 200 ~ 400nm.
Wherein, the preparation method of the first colloidal sol is as follows:
Step s311, by alkali lye and organic solvent mixing, and stirs acquisition solution A at the temperature of 20 ~ 80 DEG C.
Alkali lye can adopt weight concentration be 30% ammoniacal liquor, NaOH or potassium hydroxide solution, organic solvent can adopt absolute ethyl alcohol, absolute methanol or anhydrous propanone.The volume ratio of alkali lye and organic solvent is 1: 10 ~ 20.
Step s312, add in solution A after being diluted by silicone grease with organic solvent, temperature is remained on 20 ~ 80 DEG C, the mol ratio of the alkali in silicone grease and alkali lye is: 0.5 ~ 3 simultaneously.
Diluted by silicone grease with organic solvent (as absolute ethyl alcohol, absolute methanol or anhydrous propanone), then add the solution A that step s311 obtains, the temperature of solution A is remained on 20 ~ 80 DEG C simultaneously, the mol ratio of the alkali in silicone grease and alkali lye is 0.5 ~ 3.
Step s313, stirs solution A 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm.
Stir solution A, mixing speed is 20 ~ 300 revs/min, and mixing time is 20 ~ 200 minutes, thus obtains the first colloidal sol.In the first colloidal sol, the particle diameter of silica dioxide granule is 10 ~ 100nm.
The preparation method of the second colloidal sol is as follows:
Second colloidal sol processes acquisition further to the first colloidal sol, namely obtains on the basis of the first colloidal sol.Therefore, step s311, the step s312 of the second colloidal sol and step s313 identical with step s311, step s312 and the step s313 in the first colloidal sol making step.
Step s314, is mixed into C solution by alkali lye, the first colloidal sol and organic solvent at the temperature of 20 ~ 80 DEG C.
Get mass concentration be 30% alkali lye (as ammoniacal liquor, NaOH or potassium hydroxide solution), the first colloidal sol and organic solvent (absolute ethyl alcohol, absolute methanol or anhydrous propanone) at the temperature of 20 ~ 80 DEG C, be uniformly mixed into C solution.The mol ratio of the silica in the alkali in alkali lye and the first colloidal sol is 0.5 ~ 3.
Step s315, to add in described C solution after described silicone grease dilution with organic solvent, stir described solution 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, to make silica dioxide granule grow up, thus acquisition includes the second colloidal sol that particle diameter is the silica dioxide granule of 200 ~ 400nm.
To add in described C solution after the dilution of described silicone grease with organic solvent, silicone grease be 0.5 ~ 2 with the mol ratio of the silica dioxide granule in the first colloidal sol, then stirs and silica dioxide granule is grown up to 200 ~ 400nm, thus acquisition the second colloidal sol.
Step s32, adds coupling agent respectively in described first colloidal sol and the second colloidal sol, mutually bonds to make the silica dioxide granule in described first colloidal sol and the second colloidal sol.
Add coupling agent respectively in the first colloidal sol and the second colloidal sol, the mass percent that the addition of coupling agent accounts for whole system is 0.1 ~ 1, mutually bonds to make the silica dioxide granule in the first colloidal sol and the second colloidal sol.Coupling agent can be KH-550, KH-560, KH-570, KH792, the one in DL602, DL171, A-151.
Step s33, is adjusted to 2 ~ 4 by the pH value of the first colloidal sol and the second colloidal sol.
Add anhydrous acid, as glacial acetic acid, fuming nitric aicd or phosphoric acid, so that the pH value of the first colloidal sol and the second colloidal sol is adjusted to 2 ~ 4.
Step s34, by the first colloidal sol and the mixing of the second colloidal sol, obtains the aggregate that small particle-size silica particle surrounds Large stone silica dioxide granule.
By the first colloidal sol and the mixing of the second colloidal sol, the mass ratio of the first colloidal sol and the mixing of the second colloidal sol is 1 ~ 10, make small particle-size silica particle in the first colloidal sol and the Large stone silica dioxide granule surrounded in the second colloidal sol by self assembly effect, thus form sub-micron-nanostructured and be similar to Mastoid aggregate.The particle diameter of aggregate is less than visible wavelength range.
Step s35, is coated in the surface of resin bed by aggregate.
By to lift or aggregate to be coated in the surface of resin bed by the means such as spraying, to make silica dioxide granule be similar to " plantation " on the glass substrate, thus form micro nano structure layer.Micro nano structure layer thickness is less than or equal to more than 600nm.
Step s40, makes described resin bed solidify to form resin bed, makes described micro nano structure layer and described glass bond together simultaneously.
Under the glass being coated with resin bed and micro nano structure layer being placed on the temperature of 20 ~ 180 DEG C, insulation solidify to form resin bed in 30 ~ 450 minutes.
Step s50, makes hydrophobic decorative layer on the surface of micro nano structure layer.
Step s51, mixes hydrophobic modifier with solvent, obtains the hydrophobic modifier solution that mass concentration is 0.1 ~ 5%.
Hydrophobic modifier is mixed with solvent, and the mass concentration of hydrophobic modifier is controlled 0.1 ~ 5%.Hydrophobic modifier can adopt the mixing of one or more in trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane, perfluoroalkyl alkoxy silane.Solvent can adopt absolute ethyl alcohol, cyclohexane or isopropyl alcohol.
Step s52, is coated in the surface of micro nano structure layer by hydrophobic modifier.
Czochralski method, spraying process or knife coating is adopted hydrophobic modifier to be coated in equably the surface of micro nano structure layer.
Step s53, places 5 ~ 72 hours at normal temperatures, obtains hydrophobic decorative layer.
Hydrophobic decorative layer is placed at normal temperatures and within 5 ~ 72 hours, makes it solidify, to improve the adhesion strength of hydrophobic decorative layer.
Introduce the manufacturing process of super-hydrophobic glass below by way of example in detail.
Embodiment one
The aliphatic amine of the epoxy resin of 60 weight portions, 1 weight portion, the KH-550 of 0.05 weight portion are added mixing in the dimethyl formamide of 100 weight portions and obtain resin solution.By the resin solution of mechanical blade coating mode at glass basic surface coating 10nm.
Be that the ammoniacal liquor of 30% mixes with the absolute ethyl alcohol of 20mL by 1mL mass concentration, stir at the temperature of 20 ~ 80 DEG C and obtain solution A.Add in solution A after 1mL being analyzed the dilution of pure silester with absolute ethyl alcohol, the mol ratio of the alkali in ethyl orthosilicate and alkali lye is 0.5, the temperature of solution A is remained on 20 ~ 80 DEG C, stir 200 minutes at 20 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm; In the first colloidal sol, add KH-550, mutually bond to make the silica dioxide granule in the first colloidal sol; With anhydrous glacial acetic acid, the pH value of the first colloidal sol is adjusted to 2.
Get that 1mL mass concentration is the ammoniacal liquor of 30%, first colloidal sol of 0.5mL and 20mL absolute ethyl alcohol be mixed into C solution at the temperature of 20 DEG C; Add in C solution after the ethyl orthosilicate of 0.8mL being diluted with absolute ethyl alcohol, silica dioxide granule is grown up to 200 ~ 400nm, thus obtains the second colloidal sol; In the second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.1% of the first colloidal sol and the second colloidal sol gross weight, mutually bonds to make the silica dioxide granule in the second colloidal sol; With anhydrous glacial acetic acid, the pH value of the second colloidal sol is adjusted to 2.
By the first colloidal sol and the mixing of the second colloidal sol, the mass ratio of the first colloidal sol and the mixing of the second colloidal sol is 1, makes the small particle-size silica particle in the first colloidal sol and the Large stone silica dioxide granule self assembly in the second colloidal sol, forms aggregate.
By lift mode, aggregate is coated in the surface of resin bed, thus forms micro nano structure layer, the thickness of micro nano structure layer is 500nm.
The glass being coated with resin bed and micro nano structure layer is incubated 450 minutes to make resin bed solidify at the temperature of 20 DEG C.
By with absolute ethyl alcohol, trim,ethylchlorosilane is diluted to the trim,ethylchlorosilane solution that mass concentration is 0.1%, with czochralski method, trim,ethylchlorosilane is coated in the surface of micro nano structure, then place 5 hours at normal temperatures, thus obtain hydrophobic decorative layer.
Embodiment two
The aliphatic amine of the epoxy resin of 70 weight portions, 5 weight portions, the KH-550 of 0.1 weight portion are added mixing in the dimethyl formamide of 100 weight portions and obtain resin solution.By the resin solution of mechanical blade coating mode at glass basic surface coating 100nm.
Be that the ammoniacal liquor of 30% mixes with the absolute ethyl alcohol of 15mL by 1mL mass concentration, stir at the temperature of 20 ~ 80 DEG C and obtain solution A.Add in solution A after 1mL being analyzed the dilution of pure silester with absolute ethyl alcohol, the mol ratio of the alkali in ethyl orthosilicate and alkali lye is 1, the temperature of solution A is remained on 20 ~ 80 DEG C, stir 100 minutes at 50 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm; In the first colloidal sol, add KH-550, mutually bond to make the silica dioxide granule in the first colloidal sol; With anhydrous glacial acetic acid, the pH value of the first colloidal sol is adjusted to 3.
Get that 1mL mass concentration is the ammoniacal liquor of 30%, first colloidal sol of 0.5mL and 20mL absolute ethyl alcohol be mixed into C solution at the temperature of 40 DEG C; With absolute ethyl alcohol will the ethyl orthosilicate of 0.8mL dilute after add in C solution, the mol ratio of the silica in the alkali in alkali lye and the first colloidal sol is 1, and silica dioxide granule is grown up to 200 ~ 400nm, thus acquisition the second colloidal sol; In the second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.5% of the first colloidal sol and the second colloidal sol gross weight, mutually bonds to make the silica dioxide granule in the second colloidal sol; With anhydrous glacial acetic acid, the pH value of the second colloidal sol is adjusted to 3.
By the first colloidal sol and the mixing of the second colloidal sol, the mass ratio of the first colloidal sol and the mixing of the second colloidal sol is 3, makes the small particle-size silica particle in the first colloidal sol and the Large stone silica dioxide granule self assembly in the second colloidal sol, forms aggregate.
By lift mode, aggregate is coated in the surface of resin bed, thus forms micro nano structure layer, the thickness of micro nano structure layer is 400nm.
The glass being coated with resin bed and micro nano structure layer is incubated 350 minutes to make resin bed solidify at the temperature of 50 DEG C.
By with absolute ethyl alcohol, trim,ethylchlorosilane is diluted to the trim,ethylchlorosilane solution that mass concentration is 0.5%, with czochralski method, trim,ethylchlorosilane is coated in the surface of micro nano structure, then place 20 hours at normal temperatures, thus obtain hydrophobic decorative layer.
Embodiment three
The aliphatic amine of the epoxy resin of 85 weight portions, 15 weight portions, the KH-550 of 1 weight portion are added mixing in the dimethyl formamide of 100 weight portions and obtain resin solution.By the resin solution of mechanical blade coating mode at glass basic surface coating 500nm.
Be that the ammoniacal liquor of 30% mixes with the absolute ethyl alcohol of 20mL by 1mL mass concentration, stir at the temperature of 20 ~ 80 DEG C and obtain solution A.Add in solution A after 1mL being analyzed the dilution of pure silester with absolute ethyl alcohol, the mol ratio of the alkali in ethyl orthosilicate and alkali lye is 2, the temperature of solution A is remained on 20 ~ 80 DEG C, stir 50 minutes at 100 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm; In the first colloidal sol, add KH-550, mutually bond to make the silica dioxide granule in the first colloidal sol; With anhydrous glacial acetic acid, the pH value of the first colloidal sol is adjusted to 4.
Get that 1mL mass concentration is the ammoniacal liquor of 30%, first colloidal sol of 0.5mL and 20mL absolute ethyl alcohol be mixed into C solution at the temperature of 40 DEG C; With absolute ethyl alcohol will the ethyl orthosilicate of 0.8mL dilute after add in C solution, the mol ratio of the silica in the alkali in alkali lye and the first colloidal sol is 2.5, and silica dioxide granule is grown up to 200 ~ 400nm, thus acquisition the second colloidal sol; In the second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.8% of the first colloidal sol and the second colloidal sol gross weight, mutually bonds to make the silica dioxide granule in the second colloidal sol; With anhydrous glacial acetic acid, the pH value of the second colloidal sol is adjusted to 4.
By the first colloidal sol and the mixing of the second colloidal sol, the mass ratio of the first colloidal sol and the mixing of the second colloidal sol is 6, makes the small particle-size silica particle in the first colloidal sol and the Large stone silica dioxide granule self assembly in the second colloidal sol, forms aggregate.
By lift mode, aggregate is coated in the surface of resin bed, thus forms micro nano structure layer, the thickness of micro nano structure layer is 450nm.
The glass being coated with resin bed and micro nano structure layer is incubated 200 minutes to make resin bed solidify at the temperature of 100 DEG C.
By with absolute ethyl alcohol, trim,ethylchlorosilane is diluted to the trim,ethylchlorosilane solution that mass concentration is 2%, with czochralski method, trim,ethylchlorosilane is coated in the surface of micro nano structure, then place 50 hours at normal temperatures, thus obtain hydrophobic decorative layer.
Embodiment four
The aliphatic amine of the epoxy resin of 90 weight portions, 25 weight portions, the KH-550 of 1.5 weight portions are added mixing in the dimethyl formamide of 100 weight portions and obtain resin solution.By the resin solution of mechanical blade coating mode at glass basic surface coating 550nm.
Be that the ammoniacal liquor of 30% mixes with the absolute ethyl alcohol of 18mL by 1mL mass concentration, stir at the temperature of 20 ~ 80 DEG C and obtain solution A.Add in solution A after 1mL being analyzed the dilution of pure silester with absolute ethyl alcohol, the mol ratio of the alkali in ethyl orthosilicate and alkali lye is 2.5, the temperature of solution A is remained on 20 ~ 80 DEG C, stir 20 minutes at 200 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm; In the first colloidal sol, add KH-550, mutually bond to make the silica dioxide granule in the first colloidal sol; With anhydrous glacial acetic acid, the pH value of the first colloidal sol is adjusted to 3.5.
Get that 1mL mass concentration is the ammoniacal liquor of 30%, first colloidal sol of 0.5mL and 20mL absolute ethyl alcohol be mixed into C solution at the temperature of 70 DEG C; With absolute ethyl alcohol will the ethyl orthosilicate of 0.8mL dilute after add in C solution, the mol ratio of the silica in the alkali in alkali lye and the first colloidal sol is 3, and silica dioxide granule is grown up to 200 ~ 400nm, thus acquisition the second colloidal sol; In the second colloidal sol, add KH-550, the addition of KH-550 accounts for 1% of the first colloidal sol and the second colloidal sol gross weight, mutually bonds to make the silica dioxide granule in the second colloidal sol; With anhydrous glacial acetic acid, the pH value of the second colloidal sol is adjusted to 3.5.
By the first colloidal sol and the mixing of the second colloidal sol, the mass ratio of the first colloidal sol and the mixing of the second colloidal sol is 8, makes the small particle-size silica particle in the first colloidal sol and the Large stone silica dioxide granule self assembly in the second colloidal sol, forms aggregate.
By lift mode, aggregate is coated in the surface of resin bed, thus forms micro nano structure layer, the thickness of micro nano structure layer is 550nm.
The glass being coated with resin bed and micro nano structure layer is incubated 50 minutes to make resin bed solidify at the temperature of 150 DEG C.
By with absolute ethyl alcohol, trim,ethylchlorosilane is diluted to the trim,ethylchlorosilane solution that mass concentration is 4%, with czochralski method, trim,ethylchlorosilane is coated in the surface of micro nano structure, then place 60 hours at normal temperatures, thus obtain hydrophobic decorative layer.
Embodiment five
The aliphatic amine of the epoxy resin of 95 weight portions, 30 weight portions, the KH-550 of 2 weight portions are added mixing in the dimethyl formamide of 100 weight portions and obtain resin solution.By the resin solution of mechanical blade coating mode at glass basic surface coating 1000nm.
Be that the ammoniacal liquor of 30% mixes with the absolute ethyl alcohol of 18mL by 1mL mass concentration, stir at the temperature of 20 ~ 80 DEG C and obtain solution A.Add in solution A after 1mL being analyzed the dilution of pure silester with absolute ethyl alcohol, the mol ratio of the alkali in ethyl orthosilicate and alkali lye is 3, the temperature of solution A is remained on 20 ~ 80 DEG C, stir 50 minutes at 300 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm; In the first colloidal sol, add KH-550, mutually bond to make the silica dioxide granule in the first colloidal sol; With anhydrous glacial acetic acid, the pH value of the first colloidal sol is adjusted to 4.
Get that 1mL mass concentration is the ammoniacal liquor of 30%, first colloidal sol of 0.5mL and 20mL absolute ethyl alcohol be mixed into C solution at the temperature of 80 DEG C; With absolute ethyl alcohol will the ethyl orthosilicate of 0.8mL dilute after add in C solution, the mol ratio of the silica in the alkali in alkali lye and the first colloidal sol is 3, and silica dioxide granule is grown up to 200 ~ 400nm, thus acquisition the second colloidal sol; In the second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.6% of the first colloidal sol and the second colloidal sol gross weight, mutually bonds to make the silica dioxide granule in the second colloidal sol; With anhydrous glacial acetic acid, the pH value of the second colloidal sol is adjusted to 1.5.
By the first colloidal sol and the mixing of the second colloidal sol, the mass ratio of the first colloidal sol and the mixing of the second colloidal sol is 10, makes the small particle-size silica particle in the first colloidal sol and the Large stone silica dioxide granule self assembly in the second colloidal sol, forms aggregate.
By lift mode, aggregate is coated in the surface of resin bed, thus forms micro nano structure layer, the thickness of micro nano structure layer is 50nm.
The glass being coated with resin bed and micro nano structure layer is incubated 30 minutes to make resin bed solidify at the temperature of 180 DEG C.
By with absolute ethyl alcohol, trim,ethylchlorosilane is diluted to the trim,ethylchlorosilane solution that mass concentration is 5%, with czochralski method, trim,ethylchlorosilane is coated in the surface of micro nano structure, then place 72 hours at normal temperatures, thus obtain hydrophobic decorative layer.
The preparation method of super-hydrophobic glass provided by the invention first makes resin bed on the glass substrate, then " plantation " micro nano structure layer on the resin layer, the adhesion of micro nano structure layer and substrate of glass can be improved by resin bed, thus improve the wearability of micro nano structure layer, and then super-hydrophobic glass is enable to keep its hydrophobic performance for a long time.Therefore, this super-hydrophobic glass not only has excellent hydrophobicity and wearability, and can keep its hydrophobicity for a long time, thus super-hydrophobic glass is strided forward to industrialization.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (21)
1. a super-hydrophobic glass, comprise substrate of glass and be arranged on the micro nano structure layer of described glass surface, it is characterized in that, resin bed is provided with between described substrate of glass and described micro nano structure layer, to improve the adhesion between described micro nano structure layer and described substrate of glass, described micro nano structure layer is the silica agglomerates of sub-micron-nanostructured, and the particle diameter of described silica agglomerates is not more than 400nm, the silica agglomerates of described sub-micron-nanostructured comprises silica dioxide granule that particle diameter adhered to one another is 10 ~ 100nm and particle diameter is the silica dioxide granule of 200 ~ 400nm, the thickness of described micro nano structure layer is 400 ~ 500nm.
2. super-hydrophobic glass as claimed in claim 1, is characterized in that, the material component of described resin bed comprise percentage by weight be 60 ~ 95 transparent resin, percentage by weight be 1 ~ 30 curing agent and percentage by weight be the coupling agent of 0.05 ~ 2.
3. super-hydrophobic glass as claimed in claim 2, it is characterized in that, described transparent resin is epoxy resin, unsaturated-resin or phenolic resins.
4. super-hydrophobic glass as claimed in claim 2, it is characterized in that, described curing agent is aliphatic amine, aromatic amines, amide groups amine, hide solidification amine or urea substitute.
5. super-hydrophobic glass as claimed in claim 2, it is characterized in that, described coupling agent is KH-550, KH-560, KH-570, KH792, DL602, DL171, A-151.
6. super-hydrophobic glass as claimed in claim 1, it is characterized in that, the thickness of described resin bed is 10 ~ 1000nm.
7. super-hydrophobic glass as claimed in claim 1, it is characterized in that, also be provided with hydrophobic decorative layer on the surface of described micro nano structure layer, described hydrophobic decorative layer adopts trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane or perfluoroalkyl alkoxy silane to make.
8. a preparation method for super-hydrophobic glass, is characterized in that, comprises the following steps:
Make resin solution;
Described resin solution is coated in glass basic surface and forms resin bed;
Make micro nano structure layer on the surface of described resin bed, described micro nano structure layer is the silica agglomerates of sub-micron-nanostructured, and the particle diameter of described silica agglomerates is not more than 400nm;
Described resin bed is solidified, make described micro nano structure layer and described glass bond together simultaneously, the silica agglomerates of described sub-micron-nanostructured comprises silica dioxide granule that particle diameter adhered to one another is 10 ~ 100nm and particle diameter is the silica dioxide granule of 200 ~ 400nm, and the thickness of described micro nano structure layer is 400 ~ 500nm.
9. preparation method as claimed in claim 8, it is characterized in that, described resin solution obtains in the following manner: namely, the curing agent of the transparent resin of 60 ~ 95 weight portions, 1 ~ 30 weight portion, the coupling agent of 0.05 ~ 2 weight portion added in the solvent of 100 ~ 1000 weight portions and mix.
10. preparation method as claimed in claim 9, is characterized in that, described transparent resin adopts the one in epoxy resin, unsaturated-resin or phenolic resins.
11. preparation methods as claimed in claim 9, is characterized in that, the one that described curing agent adopts aliphatic amine, aromatic amines, amide groups amine, hides in solidification amine or urea substitute.
12. preparation methods as claimed in claim 9, is characterized in that, described coupling agent adopts KH-550, KH-560, KH-570, KH792, the one in DL602, DL171, A-151.
13. preparation methods as claimed in claim 8, is characterized in that, the thickness of the described resin bed applied at described glass basic surface is 10 ~ 1000nm, and thickness difference is less than 500nm.
14. preparation methods as claimed in claim 8, is characterized in that, the step making micro nano structure layer on the surface of described resin bed comprises:
Formed by silicone grease hydrolysis and comprise the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm, and include the second colloidal sol that particle diameter is the silica dioxide granule of 200 ~ 400nm;
In described first colloidal sol and the second colloidal sol, add coupling agent respectively, mutually bond to make the silica dioxide granule in described first colloidal sol and the second colloidal sol;
The pH value of described first colloidal sol and the second colloidal sol is regulated to be 2 ~ 4;
By described first colloidal sol and the mixing of the second colloidal sol, obtain the aggregate of sub-micron-nanostructured;
Described aggregate is coated in the surface of described resin bed.
15. preparation methods as claimed in claim 14, is characterized in that, be hydrolyzed obtain that to include particle diameter be that the step of described first colloidal sol of the silica dioxide granule of 10 ~ 100nm comprises by described silicone grease:
By alkali lye and organic solvent mixing, and at the temperature of 20 ~ 80 DEG C, stir acquisition solution;
With organic solvent by adding in described solution after the dilution of described silicone grease, make the temperature of described solution remain on 20 ~ 80 DEG C, the mol ratio of the alkali in described silicone grease and described alkali lye is: 0.5 ~ 3 simultaneously;
Stir described solution 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm.
16. preparation methods as claimed in claim 14, is characterized in that, be hydrolyzed obtain that to include particle diameter be that the step of described second colloidal sol of the silica dioxide granule of 200 ~ 400nm comprises by described silicone grease:
By alkali lye and organic solvent mixing, and at the temperature of 20 ~ 80 DEG C, stir acquisition solution;
With organic solvent by adding in described solution after the dilution of described silicone grease, temperature is remained on 20 ~ 80 DEG C, the mol ratio of the alkali in described silicone grease and described alkali lye is: 0.5 ~ 3 simultaneously;
Stir described solution 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, thus acquisition includes the first colloidal sol that particle diameter is the silica dioxide granule of 10 ~ 100nm;
Alkali lye, the first colloidal sol and organic solvent are mixed into C solution at the temperature of 20 ~ 80 DEG C;
To add in described C solution after described silicone grease dilution with organic solvent, described solution is stirred 20 ~ 200 minutes with the speed of 20 ~ 300 revs/min, to make described silica dioxide granule grow up, thus acquisition includes described second colloidal sol that particle diameter is the silica dioxide granule of 200 ~ 400nm.
17. preparation methods as claimed in claim 14, it is characterized in that, described silicone grease is ethyl orthosilicate or butyl silicate.
18. preparation methods as described in claim 15 or 16, it is characterized in that, described alkali lye is ammoniacal liquor, NaOH or potassium hydroxide.
19. preparation methods as described in claim 15 or 16, it is characterized in that, described organic solvent is ethanol, methyl alcohol or acetone.
20. preparation methods as claimed in claim 8, is characterized in that, described resin bed is that insulation solidify to form resin bed in 30 ~ 450 minutes at the temperature of 20 ~ 180 DEG C.
21. preparation methods as claimed in claim 8, it is characterized in that, the thickness of described micro nano structure layer is less than or equal to 600nm.
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| CN103204639B (en) * | 2013-04-19 | 2016-06-01 | 奇瑞汽车股份有限公司 | The preparation method of dustproof automotive glass |
| CN103468047A (en) * | 2013-09-20 | 2013-12-25 | 云南银峰新材料有限公司 | Preparation method of composite nanometer SiO2 double-hydrophobic coating |
| CN103552546A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨固泰电子有限责任公司 | Super-hydrophobic defogging automobile glass |
| CN104015431B (en) * | 2014-06-20 | 2016-08-24 | 苏州苏大维格光电科技股份有限公司 | Protection glass of nano self-cleaning and actively anti-fog function and preparation method thereof |
| CN104692672B (en) * | 2015-02-08 | 2017-08-18 | 扬州明晟新能源科技有限公司 | A kind of anti-reflection anti-dazzle liquid of LED glass lamp shades and preparation method thereof |
| CN105070847B (en) * | 2015-09-10 | 2017-10-17 | 京东方科技集团股份有限公司 | A kind of composite bed, its preparation method and OLED |
| CN105176150B (en) * | 2015-10-27 | 2017-10-10 | 华北电力大学（保定） | A kind of resistance to knife cuts the preparation method of the transparent hydrophobic coating of acid-alkali-corrosive-resisting |
| CN107603284B (en) * | 2017-07-27 | 2020-05-05 | 武汉理工大学 | Method for preparing super-hydrophobic film by utilizing pore-forming and enhancing effects of polymerizable organic molecules |
| CN109678559A (en) * | 2018-12-25 | 2019-04-26 | 同济大学 | A kind of super-hydrophobic, Gao Naijiu Anti-seepage air-permeable sand and preparation method thereof |
| CN110467830B (en) * | 2019-07-23 | 2021-11-09 | 北京易净星科技有限公司 | Wear-resistant hydrophobic coating and method for preparing same |
| CN111718603B (en) * | 2020-07-01 | 2021-09-10 | 中国石油大学(北京) | Silicon dioxide surface modification method |
| CN113980576B (en) * | 2021-12-02 | 2022-09-09 | 大连理工大学 | Preparation method of anti-icing durable super-hydrophobic coating |
| CN114477790B (en) * | 2021-12-24 | 2024-03-15 | 中建材玻璃新材料研究院集团有限公司 | Long-acting hydrophobic coating for glass and preparation method thereof |
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| EP2130878B1 (en) * | 2008-06-05 | 2011-04-20 | iGUZZINI ILLUMINAZIONE S.p.A. | Double layer coating, its preparation and its use for rendering ultra water-repellent and antireflective the surfaces to which it is applied |
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