CN102501477A - Super-hydrophobic glass and manufacturing method thereof - Google Patents
Super-hydrophobic glass and manufacturing method thereof Download PDFInfo
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- CN102501477A CN102501477A CN2011103069024A CN201110306902A CN102501477A CN 102501477 A CN102501477 A CN 102501477A CN 2011103069024 A CN2011103069024 A CN 2011103069024A CN 201110306902 A CN201110306902 A CN 201110306902A CN 102501477 A CN102501477 A CN 102501477A
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 50
- 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 75
- 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 88
- 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 66
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- 239000002245 particle Substances 0.000 claims description 42
- 230000002209 hydrophobic effect Effects 0.000 claims description 35
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- 238000002360 preparation method Methods 0.000 claims description 29
- 239000004519 grease Substances 0.000 claims description 26
- 229920001296 polysiloxane Polymers 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 23
- 239000012895 dilution Substances 0.000 claims description 20
- 238000010790 dilution Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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
- 239000000377 silicon dioxide Substances 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
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 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
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- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 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
- 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
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- 238000002834 transmittance Methods 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 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
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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
Automobile popularize and skyscraper increase the favor that makes glass obtain market with self-cleaning function.Typical self-cleaning glass is to utilize the automatically cleaning material to make a self-cleaning film at glass surface, prevents that by self-cleaning film contamination by dust, sleet are bonded in glass surface, can also suppress microorganism adhering at glass surface simultaneously.
Common self-cleaning film comprises hydrophilic film and hydrophobic film.Wherein, the contact angle of hydrophilic film requirement and water is less than 10 °, and its hydrophilicity stems from the hydroxyl of the photocatalysis generation of film.When the preparation hydrophilic film, need carry out high-temperature baking technology.The contact angle of hydrophobic film requirement and water is greater than 90 °, 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 bigger air entrapment rate, and low-surface-energy can reduce the adhesiveness of film and water droplet.
Compare with hydrophilic film, hydrophobic film has the following advantages: the first, can obtain hydrophobic film at normal temperatures and pressures, thus the adverse effect that can avoid high-temperature baking to cause glass basis; The second, resistance to soiling is outstanding, and its hydrophobicity can avoid glass to contact with corrosion solvents such as strong acid, highly basic, reductant-oxidants as far as possible, thereby can reduce the destruction that deep-etching solution possibly cause glass.Therefore, it is extensive to have a self-cleaning glass application prospect of hydrophobic function.
Yet the wearability of existing hydrophobic film is relatively poor, and the as easy as rolling off a log hydrophobicity of self-cleaning glass that causes of the wearing and tearing in the use reduces, and this makes hydrophobic self-cleaning glass never have industrialization.In addition, the surface roughness of film is a mutual restriction to the transparency and the hydrophobic influence of film.The increase of surface roughness must increase light scattering in the communication process in film.Therefore, on the one hand, thin-film hydrophobic property is owing to the increase of surface roughness strengthens; 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, thereby can make super-hydrophobic glass keep its hydrophobicity for a long time.
In order to achieve the above object; The present invention proposes a kind of super-hydrophobic glass; The micro nano structure layer that comprises substrate of glass and be arranged on said glass surface; Between said substrate of glass and said micro nano structure layer, be provided with resin bed, to improve the adhesion between said micro nano structure layer and the said substrate of glass.
Preferably, the material component of said resin bed comprises that percentage by weight is that 60～95 transparent resin, percentage by weight are that 1～30 curing agent and percentage by weight are 0.05～2 coupling agent.
Preferably, said transparent resin is epoxy resin, unsaturated-resin or phenolic resins.
Preferably, said curing agent is aliphatic amine, aromatic amines, amide groups amine, hides and solidify amine or urea substitute.
Preferably, said coupling agent is KH-550, KH-560, KH-570, KH792, DL602, DL171, A-151.
Preferably, the thickness of said resin bed is 10～1000nm.
Preferably, the silica aggregate that said micro nano structure layer is sub-micron-nanostructured, and also the particle diameter of said silica aggregate is not more than 400nm.
Preferably, also be provided with the hydrophobic decorative layer on the surface of said micro nano structure layer, said 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, may further comprise the steps: preparing resin solution; Said resin solution is coated in glass basic surface forms resin bed; Surface at said resin bed makes the micro nano structure layer; Said resin bed is solidified, said micro nano structure layer and said glass are bonded together.
Preferably, said resin solution is to obtain in the following manner: promptly, the coupling agent of the curing agent of the transparent resin of 60～95 weight portions, 1～30 weight portion, 0.05～2 weight portion is added in the solvent of 100～1000 weight portions and mix.
Preferably, said transparent resin adopts a kind of in epoxy resin, unsaturated-resin or the phenolic resins.
Preferably, said curing agent adopts aliphatic amine, aromatic amines, amide groups amine, hides and solidify a kind of in amine or the urea substitute.
Preferably, said coupling agent adopts KH-550, KH-560, KH-570, KH792, DL602, a kind of among DL171, the A-151.
Preferably, the thickness of the said resin bed that applies at said glass basic surface is 10～1000nm, and thickness difference is less than 500nm.
Preferably; The step of making the micro nano structure layer on the surface of said resin bed comprises: comprise first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm through silicone grease hydrolysis formation, and include second colloidal sol that particle diameter is the silica dioxide granule of 200～400nm; In said first colloidal sol and second colloidal sol, add coupling agent respectively, so that the silica dioxide granule in said first colloidal sol and second colloidal sol bonds each other; The pH value of regulating said first colloidal sol and second colloidal sol is 2～4; Said first colloidal sol and second colloidal sol are mixed, obtain the aggregate of sub-micron-nanostructured; Said aggregate is coated in the surface of said resin bed.
Preferably, obtaining to include particle diameter by said silicone grease hydrolysis is that the step of said first colloidal sol of the silica dioxide granule of 10～100nm comprises: alkali lye and organic solvent are mixed, and under 20～80 ℃ temperature, stir acquisition solution; With organic solvent said silicone grease dilution back is added in the said solution, make the temperature of said solution remain on 20～80 ℃ simultaneously, the mol ratio of the alkali in said silicone grease and the said alkali lye is: 0.5～3; Stir said solution 20～200 minutes with 20～300 rev/mins speed, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm.
Preferably, obtaining to include particle diameter by said silicone grease hydrolysis is that the step of said second colloidal sol of the silica dioxide granule of 200～400nm comprises: alkali lye and organic solvent are mixed, and under 20～80 ℃ temperature, stir acquisition solution; With organic solvent said silicone grease dilution back is added in the said solution, simultaneously temperature is remained on 20～80 ℃, the mol ratio of the alkali in said silicone grease and the said alkali lye is: 0.5～3; Stir said solution 20～200 minutes with 20～300 rev/mins speed, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm; Alkali lye, first colloidal sol and organic solvent are mixed into C solution under 20～80 ℃ temperature; With organic solvent said silicone grease dilution back is added in the said C solution; Stirred said solution 20～200 minutes with 20～300 rev/mins speed; So that said silica dioxide granule grows up, thereby obtain to include said second colloidal sol that particle diameter is the silica dioxide granule of 200～400nm.
Preferably, said silicone grease is ethyl orthosilicate or butyl silicate.
Preferably, said alkali lye is ammoniacal liquor, NaOH or potassium hydroxide.
Preferably, said organic solvent is ethanol, methyl alcohol or acetone.
Preferably, said resin bed is under 20～180 ℃ temperature, to be incubated 30～450 minutes to solidify to form resin bed.
Preferably, the thickness of said 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 is provided with 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; Thereby improve the wearability of micro nano structure layer, thereby make super-hydrophobic glass can keep its hydrophobicity for a long time.Therefore, this super-hydrophobic glass not only has good hydrophobicity, and can keep its hydrophobicity for a long time, thereby makes super-hydrophobic glass stride forward to industrialization.
As a preferred embodiment of the present invention; The size of the micro nano structure layer in the super-hydrophobic glass is not more than wavelength of visible light, promptly is less than or equal to 400nm, and this can reduce the scattered power of visible light when seeing through the micro nano structure layer; Thereby make the surface roughness of micro nano structure layer and visible light transmittance rate obtain good balance; And then the contact angle that makes super-hydrophobic glass is greater than 150 °, and roll angle is less than 10 °, and the light transmittance of visible light can reach more than 85%.
Similarly; The preparation method of super-hydrophobic glass provided by the invention is a preparing resin layer at first on substrate of glass; " plantation " micro nano structure layer on resin bed then; Can improve the adhesion of micro nano structure layer and substrate of glass by resin bed, thereby improve the wearability of micro nano structure layer, and then make super-hydrophobic glass can keep its hydrophobic performance for a long time.Therefore, this super-hydrophobic glass not only has good hydrophobicity and wearability, and can keep its hydrophobicity for a long time, thereby makes super-hydrophobic glass stride forward to industrialization.
As a preferred embodiment of the present invention; Preparation method through silica dioxide granule provided by the invention; Prepare silica dioxide granule sub-micron-nanostructured, the reunion shape; And the particle diameter that makes silica dioxide granule is less than 400nm, thus the scattering can reduce light and in the micro nano structure layer, propagate the time, and then improve the transparency of super-hydrophobic glass.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work property, can also obtain other accompanying drawing 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.
The specific embodiment
For making those skilled in the art understand technical scheme of the present invention better, super-hydrophobic glass that the present invention is proposed below in conjunction with accompanying drawing and preparation method thereof is described in detail.
Fig. 1 is the sectional view of super-hydrophobic glass provided by the invention.See also Fig. 1, the super-hydrophobic glass that 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, preferred 100～400nm.The material component of resin bed 2 comprises that percentage by weight is that 60～95 transparent resin, percentage by weight are that 1～30 curing agent and percentage by weight are 0.05～2 coupling agent.Wherein,
Transparent resin can adopt epoxy resin, unsaturated-resin or phenolic resins.Curing agent can adopt aliphatic amine, aromatic amines, amide groups amine, hide and solidify 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 a silica micro nano structure layer, and the size of silica micro nano structure is not more than visible wavelength; Promptly be less than or equal to 400nm; This can reduce the scattered power of visible light when seeing through micro nano structure layer 3, thereby makes the surface roughness and the good balance of visible light transmittance rate acquisition of micro nano structure layer 3, and then the contact angle that makes super-hydrophobic glass is greater than 150 °; Roll angle is less than 10 °, and the light transmittance of visible light can reach more than 85%.The thickness of micro nano structure layer 3 is no more than 600nm, preferred 400～500nm.
Hydrophobic decorative layer 4 adopts trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane or perfluoroalkyl alkoxy silane material.
The super-hydrophobic glass that present embodiment provides is provided with resin bed between substrate of glass and micro nano structure layer, with the wearability of raising micro nano structure layer, thereby make super-hydrophobic glass can keep its hydrophobicity for a long time.Therefore, this super-hydrophobic glass not only has good hydrophobicity and wearability, and can keep its hydrophobicity for a long time, thereby makes super-hydrophobic glass stride forward to industrialization.
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.See also Fig. 2, the preparation method of super-hydrophobic glass may further comprise the steps:
Step s10, preparing resin solution.
Resin solution is to mix in the solvent with coupling agent adding 100～1000 weight portions of the curing agent of the transparent resin of 60～95 weight portions, 1～30 weight portion, 0.05～2 weight portion.Wherein, transparent resin adopts a kind of in epoxy resin, unsaturated-resin or the phenolic resins.Curing agent adopts aliphatic amine, aromatic amines, amide groups amine, hide and solidify a kind of in amine or the urea substitute.Coupling agent adopts KH-550, KH-560, KH-570, KH792, DL602, a kind of among DL171, the A-151.Solvent adopts a kind of in dimethyl formamide, three oxygen ethene, ethylene glycol phenyl ether, the xylenes.
Step s20, the surface that resin solution is coated in substrate of glass is to form resin bed.
Adopt manual blade coating, mechanical blade coating, high frequency sieve to tremble existing processes such as coating, the surface that will be coated in substrate of glass through the resin solution that step s10 makes is to form resin bed.The thickness of the resin bed that applies at glass basic surface is 10～1000nm, and thickness difference is less than 500nm.
Step s30 makes the micro nano structure layer on the surface of resin bed.
The manufacturing process of micro nano structure layer may further comprise the steps:
Step s31 comprises first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm through silicone grease hydrolysis formation, and includes second colloidal sol that particle diameter is the silica dioxide granule of 200～400nm.
Wherein, the preparation method of first colloidal sol is following:
Step s311 mixes alkali lye and organic solvent, and under 20～80 ℃ temperature, stirs acquisition A solution.
It is 30% ammoniacal liquor, NaOH or potassium hydroxide solution that alkali lye can adopt weight concentration, and organic solvent can adopt absolute ethyl alcohol, absolute methanol or anhydrous propanone.Alkali lye is 1: 10～20 with the volume of organic solvent ratio.
Step s312 adds silicone grease dilution back in the A solution with organic solvent, simultaneously temperature is remained on 20～80 ℃, and the mol ratio of the alkali in silicone grease and the alkali lye is: 0.5～3.
With the silicone grease dilution, add the A solution that step s311 obtains with organic solvent (like absolute ethyl alcohol, absolute methanol or anhydrous propanone) then, the temperature with A solution remains on 20～80 ℃ simultaneously, and the mol ratio of the alkali in silicone grease and the alkali lye is 0.5～3.
Step s313 stirred A solution 20～200 minutes with 20～300 rev/mins speed, thereby obtained to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm.
Stir A solution, mixing speed is 20～300 rev/mins, and mixing time is 20～200 minutes, thereby obtains first colloidal sol.The particle diameter of silica dioxide granule is 10～100nm in first colloidal sol.
The preparation method of second colloidal sol is following:
Second colloidal sol is further processed acquisition to first colloidal sol, promptly on the basis of first colloidal sol, obtains.Therefore, the step s311 of second colloidal sol, step s312 and step s313 are identical with step s311, step s312 and step s313 in the first colloidal sol making step.
Step s314 is mixed into C solution with alkali lye, first colloidal sol and organic solvent under 20～80 ℃ temperature.
Get mass concentration and be 30% alkali lye (like ammoniacal liquor, NaOH or potassium hydroxide solution), first colloidal sol and organic solvent (absolute ethyl alcohol, absolute methanol or anhydrous propanone) and under 20～80 ℃ temperature, mix into C solution.The mol ratio of the silica in the alkali in the alkali lye and first colloidal sol is 0.5～3.
Step s315; With organic solvent said silicone grease dilution back is added in the said C solution; Stirred said solution 20～200 minutes with 20～300 rev/mins speed,, thereby obtain to include second colloidal sol that particle diameter is the silica dioxide granule of 200～400nm so that silica dioxide granule grows up.
With organic solvent said silicone grease dilution back is added in the said C solution, the mol ratio of the silica dioxide granule in the silicone grease and first colloidal sol is 0.5～2, stirs then silica dioxide granule is grown up to 200～400nm, thereby obtains second colloidal sol.
Step s32 adds coupling agent respectively in said first colloidal sol and second colloidal sol, so that the silica dioxide granule in said first colloidal sol and second colloidal sol bonds each other.
In first colloidal sol and second colloidal sol, add coupling agent respectively, the mass percent that the addition of coupling agent accounts for whole system is 0.1～1, so that the silica dioxide granule in first colloidal sol and second colloidal sol bonds each other.Coupling agent can be KH-550, KH-560, KH-570, KH792, DL602, a kind of among DL171, the A-151.
Step s33 is adjusted to 2～4 with the pH value of first colloidal sol and second colloidal sol.
Add anhydrous acid,, be adjusted to 2～4 with pH value with first colloidal sol and second colloidal sol like glacial acetic acid, fuming nitric aicd or phosphoric acid.
Step s34 mixes first colloidal sol and second colloidal sol, obtains the aggregate that the small particle diameter silica dioxide granule surrounds big particle diameter silica dioxide granule.
First colloidal sol and second colloidal sol are mixed; The mass ratio that first colloidal sol and second colloidal sol mix is 1～10; Make small particle diameter silica dioxide granule and the big particle diameter silica dioxide granule that surrounds in second colloidal sol in first colloidal sol through the 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 aggregate on the surface of resin bed.
Through lifting or means such as spraying are coated in the surface of resin bed with aggregate,, thereby form the micro nano structure layer so that silica dioxide granule is similar to " plantation " on substrate of glass.The micro nano structure layer thickness is less than or equal to above 600nm.
Step s40 makes said resin bed solidify to form resin bed, and said micro nano structure layer and said glass are bonded together.
The glass that is coated with resin bed and micro nano structure layer is placed on is incubated 30～450 minutes under 20～180 ℃ the temperature and solidify to form resin bed.
Step s50 makes the hydrophobic decorative layer on the surface of micro nano structure layer.
Step s51, with hydrophobic dressing agent and solvent, the acquisition mass concentration is 0.1～5% hydrophobic dressing agent solution.
With hydrophobic dressing agent and solvent, and the mass concentration of hydrophobic dressing agent is controlled at 0.1～5%.The hydrophobic dressing agent can adopt one or more the mixing in trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane, the perfluoroalkyl alkoxy silane.Solvent can adopt absolute ethyl alcohol, cyclohexane or isopropyl alcohol.
Step s52 is coated in the hydrophobic dressing agent on the surface of micro nano structure layer.
Adopt czochralski method, spraying process or knife coating the hydrophobic dressing agent to be coated in equably the surface of micro nano structure layer.
Step s53 placed 5～72 hours at normal temperatures, obtained the hydrophobic decorative layer.
The hydrophobic decorative layer placed at normal temperatures it is solidified, to improve the adhesion strength of hydrophobic decorative layer.
Introduce the manufacturing process of super-hydrophobic glass below in detail with by way of example.
Embodiment one
The KH-550 of the aliphatic amine of 60 parts by weight of epoxy resin, 1 weight portion, 0.05 weight portion is added mix in the dimethyl formamide of 100 weight portions and obtain resin solution.Apply the resin solution of 10nm at glass basic surface through mechanical blade coating mode.
Be that 30% ammoniacal liquor mixes with the absolute ethyl alcohol of 20mL with the 1mL mass concentration, under 20～80 ℃ temperature, stir and obtain A solution.With absolute ethyl alcohol 1mL being analyzed pure silester dilution back adds in the A solution; The mol ratio of the alkali in ethyl orthosilicate and the alkali lye is 0.5; The temperature of A solution is remained on 20～80 ℃; Stirred 200 minutes at 20 rev/mins, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm; In first colloidal sol, add KH-550, so that the silica dioxide granule in first colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of first colloidal sol is adjusted into 2.
Getting the 1mL mass concentration is that 30% ammoniacal liquor, first colloidal sol and the 20mL absolute ethyl alcohol of 0.5mL are mixed into C solution under 20 ℃ temperature; Add in the C solution with the ethyl orthosilicate dilution back of absolute ethyl alcohol, silica dioxide granule is grown up to 200～400nm, thereby obtain second colloidal sol 0.8mL; In second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.1% of first colloidal sol and the second colloidal sol gross weight, so that the silica dioxide granule in second colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of second colloidal sol is adjusted into 2.
First colloidal sol and second colloidal sol are mixed, and the mass ratio that first colloidal sol and second colloidal sol mix is 1, makes small particle diameter silica dioxide granule and the big particle diameter silica dioxide granule self assembly in second colloidal sol in first colloidal sol, the formation aggregate.
Through the mode of lifting aggregate is coated in the surface of resin bed, thereby forms the micro nano structure layer, the thickness of micro nano structure layer is 500nm.
The glass that is coated with resin bed and micro nano structure layer is incubated 450 minutes so that resin bed solidifies under 20 ℃ temperature.
With using absolute ethyl alcohol that trim,ethylchlorosilane is diluted to mass concentration is 0.1% trim,ethylchlorosilane solution, with czochralski method trim,ethylchlorosilane is coated in the surface of micro nano structure, places at normal temperatures then 5 hours, thereby obtains the hydrophobic decorative layer.
Embodiment two
The KH-550 of the aliphatic amine of 70 parts by weight of epoxy resin, 5 weight portions, 0.1 weight portion is added mix in the dimethyl formamide of 100 weight portions and obtain resin solution.Apply the resin solution of 100nm at glass basic surface through mechanical blade coating mode.
Be that 30% ammoniacal liquor mixes with the absolute ethyl alcohol of 15mL with the 1mL mass concentration, under 20～80 ℃ temperature, stir and obtain A solution.With absolute ethyl alcohol 1mL being analyzed pure silester dilution back adds in the A solution; The mol ratio of the alkali in ethyl orthosilicate and the alkali lye is 1; The temperature of A solution is remained on 20～80 ℃; Stirred 100 minutes at 50 rev/mins, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm; In first colloidal sol, add KH-550, so that the silica dioxide granule in first colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of first colloidal sol is adjusted into 3.
Getting the 1mL mass concentration is that 30% ammoniacal liquor, first colloidal sol and the 20mL absolute ethyl alcohol of 0.5mL are mixed into C solution under 40 ℃ temperature; Add in the C solution with the ethyl orthosilicate dilution back of absolute ethyl alcohol with 0.8mL, the mol ratio of the silica in the alkali in the alkali lye and first colloidal sol is 1, and silica dioxide granule is grown up to 200～400nm, thereby obtains second colloidal sol; In second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.5% of first colloidal sol and the second colloidal sol gross weight, so that the silica dioxide granule in second colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of second colloidal sol is adjusted into 3.
First colloidal sol and second colloidal sol are mixed, and the mass ratio that first colloidal sol and second colloidal sol mix is 3, makes small particle diameter silica dioxide granule and the big particle diameter silica dioxide granule self assembly in second colloidal sol in first colloidal sol, the formation aggregate.
Through the mode of lifting aggregate is coated in the surface of resin bed, thereby forms the micro nano structure layer, the thickness of micro nano structure layer is 400nm.
The glass that is coated with resin bed and micro nano structure layer is incubated 350 minutes so that resin bed solidifies under 50 ℃ temperature.
With using absolute ethyl alcohol that trim,ethylchlorosilane is diluted to mass concentration is 0.5% trim,ethylchlorosilane solution, with czochralski method trim,ethylchlorosilane is coated in the surface of micro nano structure, places at normal temperatures then 20 hours, thereby obtains the hydrophobic decorative layer.
Embodiment three
The KH-550 of the aliphatic amine of 85 parts by weight of epoxy resin, 15 weight portions, 1 weight portion is added mix in the dimethyl formamide of 100 weight portions and obtain resin solution.Apply the resin solution of 500nm at glass basic surface through mechanical blade coating mode.
Be that 30% ammoniacal liquor mixes with the absolute ethyl alcohol of 20mL with the 1mL mass concentration, under 20～80 ℃ temperature, stir and obtain A solution.With absolute ethyl alcohol 1mL being analyzed pure silester dilution back adds in the A solution; The mol ratio of the alkali in ethyl orthosilicate and the alkali lye is 2; The temperature of A solution is remained on 20～80 ℃; Stirred 50 minutes at 100 rev/mins, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm; In first colloidal sol, add KH-550, so that the silica dioxide granule in first colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of first colloidal sol is adjusted into 4.
Getting the 1mL mass concentration is that 30% ammoniacal liquor, first colloidal sol and the 20mL absolute ethyl alcohol of 0.5mL are mixed into C solution under 40 ℃ temperature; Add in the C solution with the ethyl orthosilicate dilution back of absolute ethyl alcohol with 0.8mL, the mol ratio of the silica in the alkali in the alkali lye and first colloidal sol is 2.5, and silica dioxide granule is grown up to 200～400nm, thereby obtains second colloidal sol; In second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.8% of first colloidal sol and the second colloidal sol gross weight, so that the silica dioxide granule in second colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of second colloidal sol is adjusted into 4.
First colloidal sol and second colloidal sol are mixed, and the mass ratio that first colloidal sol and second colloidal sol mix is 6, makes small particle diameter silica dioxide granule and the big particle diameter silica dioxide granule self assembly in second colloidal sol in first colloidal sol, the formation aggregate.
Through the mode of lifting aggregate is coated in the surface of resin bed, thereby forms the micro nano structure layer, the thickness of micro nano structure layer is 450nm.
The glass that is coated with resin bed and micro nano structure layer is incubated 200 minutes so that resin bed solidifies under 100 ℃ temperature.
With using absolute ethyl alcohol that trim,ethylchlorosilane is diluted to mass concentration is 2% trim,ethylchlorosilane solution, with czochralski method trim,ethylchlorosilane is coated in the surface of micro nano structure, places at normal temperatures then 50 hours, thereby obtains the hydrophobic decorative layer.
Embodiment four
The KH-550 of the aliphatic amine of 90 parts by weight of epoxy resin, 25 weight portions, 1.5 weight portions is added mix in the dimethyl formamide of 100 weight portions and obtain resin solution.Apply the resin solution of 550nm at glass basic surface through mechanical blade coating mode.
Be that 30% ammoniacal liquor mixes with the absolute ethyl alcohol of 18mL with the 1mL mass concentration, under 20～80 ℃ temperature, stir and obtain A solution.With absolute ethyl alcohol 1mL being analyzed pure silester dilution back adds in the A solution; The mol ratio of the alkali in ethyl orthosilicate and the alkali lye is 2.5; The temperature of A solution is remained on 20～80 ℃; Stirred 20 minutes at 200 rev/mins, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm; In first colloidal sol, add KH-550, so that the silica dioxide granule in first colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of first colloidal sol is adjusted into 3.5.
Getting the 1mL mass concentration is that 30% ammoniacal liquor, first colloidal sol and the 20mL absolute ethyl alcohol of 0.5mL are mixed into C solution under 70 ℃ temperature; Add in the C solution with the ethyl orthosilicate dilution back of absolute ethyl alcohol with 0.8mL, the mol ratio of the silica in the alkali in the alkali lye and first colloidal sol is 3, and silica dioxide granule is grown up to 200～400nm, thereby obtains second colloidal sol; In second colloidal sol, add KH-550, the addition of KH-550 accounts for 1% of first colloidal sol and the second colloidal sol gross weight, so that the silica dioxide granule in second colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of second colloidal sol is adjusted into 3.5.
First colloidal sol and second colloidal sol are mixed, and the mass ratio that first colloidal sol and second colloidal sol mix is 8, makes small particle diameter silica dioxide granule and the big particle diameter silica dioxide granule self assembly in second colloidal sol in first colloidal sol, the formation aggregate.
Through the mode of lifting aggregate is coated in the surface of resin bed, thereby forms the micro nano structure layer, the thickness of micro nano structure layer is 550nm.
The glass that is coated with resin bed and micro nano structure layer is incubated 50 minutes so that resin bed solidifies under 150 ℃ temperature.
With using absolute ethyl alcohol that trim,ethylchlorosilane is diluted to mass concentration is 4% trim,ethylchlorosilane solution, with czochralski method trim,ethylchlorosilane is coated in the surface of micro nano structure, places at normal temperatures then 60 hours, thereby obtains the hydrophobic decorative layer.
Embodiment five
The KH-550 of the aliphatic amine of 95 parts by weight of epoxy resin, 30 weight portions, 2 weight portions is added mix in the dimethyl formamide of 100 weight portions and obtain resin solution.Apply the resin solution of 1000nm at glass basic surface through mechanical blade coating mode.
Be that 30% ammoniacal liquor mixes with the absolute ethyl alcohol of 18mL with the 1mL mass concentration, under 20～80 ℃ temperature, stir and obtain A solution.With absolute ethyl alcohol 1mL being analyzed pure silester dilution back adds in the A solution; The mol ratio of the alkali in ethyl orthosilicate and the alkali lye is 3; The temperature of A solution is remained on 20～80 ℃; Stirred 50 minutes at 300 rev/mins, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm; In first colloidal sol, add KH-550, so that the silica dioxide granule in first colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of first colloidal sol is adjusted into 4.
Getting the 1mL mass concentration is that 30% ammoniacal liquor, first colloidal sol and the 20mL absolute ethyl alcohol of 0.5mL are mixed into C solution under 80 ℃ temperature; Add in the C solution with the ethyl orthosilicate dilution back of absolute ethyl alcohol with 0.8mL, the mol ratio of the silica in the alkali in the alkali lye and first colloidal sol is 3, and silica dioxide granule is grown up to 200～400nm, thereby obtains second colloidal sol; In second colloidal sol, add KH-550, the addition of KH-550 accounts for 0.6% of first colloidal sol and the second colloidal sol gross weight, so that the silica dioxide granule in second colloidal sol bonds each other; With anhydrous glacial acetic acid the pH value of second colloidal sol is adjusted into 1.5.
First colloidal sol and second colloidal sol are mixed, and the mass ratio that first colloidal sol and second colloidal sol mix is 10, makes small particle diameter silica dioxide granule and the big particle diameter silica dioxide granule self assembly in second colloidal sol in first colloidal sol, the formation aggregate.
Through the mode of lifting aggregate is coated in the surface of resin bed, thereby forms the micro nano structure layer, the thickness of micro nano structure layer is 50nm.
The glass that is coated with resin bed and micro nano structure layer is incubated 30 minutes so that resin bed solidifies under 180 ℃ temperature.
With using absolute ethyl alcohol that trim,ethylchlorosilane is diluted to mass concentration is 5% trim,ethylchlorosilane solution, with czochralski method trim,ethylchlorosilane is coated in the surface of micro nano structure, places at normal temperatures then 72 hours, thereby obtains the hydrophobic decorative layer.
The preparation method of super-hydrophobic glass provided by the invention is a preparing resin layer at first on substrate of glass; " plantation " micro nano structure layer on resin bed then; Can improve the adhesion of micro nano structure layer and substrate of glass by resin bed; Thereby improve the wearability of micro nano structure layer, and then make super-hydrophobic glass can keep its hydrophobic performance for a long time.Therefore, this super-hydrophobic glass not only has good hydrophobicity and wearability, and can keep its hydrophobicity for a long time, thereby makes super-hydrophobic glass stride forward to industrialization.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (22)
1. super-hydrophobic glass; The micro nano structure layer that comprises substrate of glass and be arranged on said glass surface; It is characterized in that, between said substrate of glass and said micro nano structure layer, be provided with resin bed, to improve the adhesion between said micro nano structure layer and the said substrate of glass.
2. super-hydrophobic glass as claimed in claim 1 is characterized in that, the material component of said resin bed comprises that percentage by weight is that 60～95 transparent resin, percentage by weight are that 1～30 curing agent and percentage by weight are 0.05～2 coupling agent.
3. super-hydrophobic glass as claimed in claim 2 is characterized in that, said transparent resin is epoxy resin, unsaturated-resin or phenolic resins.
4. super-hydrophobic glass as claimed in claim 2 is characterized in that, said curing agent is aliphatic amine, aromatic amines, amide groups amine, hides and solidify amine or urea substitute.
5. super-hydrophobic glass as claimed in claim 2 is characterized in that, said coupling agent is KH-550, KH-560, KH-570, KH792, DL602, DL171, A-151.
6. super-hydrophobic glass as claimed in claim 1 is characterized in that, the thickness of said resin bed is 10～1000nm.
7. super-hydrophobic glass as claimed in claim 1 is characterized in that, the silica aggregate that said micro nano structure layer is sub-micron-nanostructured, and also the particle diameter of said silica aggregate is not more than 400nm.
8. super-hydrophobic glass as claimed in claim 7; It is characterized in that; Surface at said micro nano structure layer also is provided with the hydrophobic decorative layer, and said hydrophobic decorative layer adopts trim,ethylchlorosilane, 17 fluorine decyl trimethoxy silanes, perfluoroalkyl chlorosilane or perfluoroalkyl alkoxy silane to make.
9. the preparation method of a super-hydrophobic glass is characterized in that, may further comprise the steps:
Preparing resin solution;
Said resin solution is coated in glass basic surface forms resin bed;
Surface at said resin bed makes the micro nano structure layer;
Said resin bed is solidified, said micro nano structure layer and said glass are bonded together.
10. preparation method as claimed in claim 9; It is characterized in that; Said resin solution is to obtain in the following manner: promptly, the coupling agent of the curing agent of the transparent resin of 60～95 weight portions, 1～30 weight portion, 0.05～2 weight portion is added in the solvent of 100～1000 weight portions and mix.
11. preparation method as claimed in claim 10 is characterized in that, said transparent resin adopts a kind of in epoxy resin, unsaturated-resin or the phenolic resins.
12. preparation method as claimed in claim 10 is characterized in that, said curing agent adopts aliphatic amine, aromatic amines, amide groups amine, hide and solidify a kind of in amine or the urea substitute.
13. preparation method as claimed in claim 10 is characterized in that, said coupling agent adopts KH-550, KH-560, KH-570, KH792, DL602, a kind of among DL171, the A-151.
14. preparation method as claimed in claim 9 is characterized in that, the thickness of the said resin bed that applies at said glass basic surface is 10～1000nm, and thickness difference is less than 500nm.
15. preparation method as claimed in claim 9 is characterized in that, the step of making the micro nano structure layer on the surface of said resin bed comprises:
Comprise first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm through silicone grease hydrolysis formation, and include second colloidal sol that particle diameter is the silica dioxide granule of 200～400nm;
In said first colloidal sol and second colloidal sol, add coupling agent respectively, so that the silica dioxide granule in said first colloidal sol and second colloidal sol bonds each other;
The pH value of regulating said first colloidal sol and second colloidal sol is 2～4;
Said first colloidal sol and second colloidal sol are mixed, obtain the aggregate of sub-micron-nanostructured;
Said aggregate is coated in the surface of said resin bed.
16. preparation method as claimed in claim 15 is characterized in that, obtaining to include particle diameter by said silicone grease hydrolysis is that the step of said first colloidal sol of the silica dioxide granule of 10～100nm comprises:
Alkali lye and organic solvent are mixed, and under 20～80 ℃ temperature, stir acquisition solution;
With organic solvent said silicone grease dilution back is added in the said solution, make the temperature of said solution remain on 20～80 ℃ simultaneously, the mol ratio of the alkali in said silicone grease and the said alkali lye is: 0.5～3;
Stir said solution 20～200 minutes with 20～300 rev/mins speed, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm.
17. preparation method as claimed in claim 15 is characterized in that, obtaining to include particle diameter by said silicone grease hydrolysis is that the step of said second colloidal sol of the silica dioxide granule of 200～400nm comprises:
Alkali lye and organic solvent are mixed, and under 20～80 ℃ temperature, stir acquisition solution;
With organic solvent said silicone grease dilution back is added in the said solution, simultaneously temperature is remained on 20～80 ℃, the mol ratio of the alkali in said silicone grease and the said alkali lye is: 0.5～3;
Stir said solution 20～200 minutes with 20～300 rev/mins speed, thereby obtain to include first colloidal sol that particle diameter is the silica dioxide granule of 10～100nm;
Alkali lye, first colloidal sol and organic solvent are mixed into C solution under 20～80 ℃ temperature;
With organic solvent said silicone grease dilution back is added in the said C solution; Stirred said solution 20～200 minutes with 20～300 rev/mins speed; So that said silica dioxide granule grows up, thereby obtain to include said second colloidal sol that particle diameter is the silica dioxide granule of 200～400nm.
18. preparation method as claimed in claim 15 is characterized in that, said silicone grease is ethyl orthosilicate or butyl silicate.
19. preparation method as claimed in claim 15 is characterized in that, said alkali lye is ammoniacal liquor, NaOH or potassium hydroxide.
20. preparation method as claimed in claim 15 is characterized in that, said organic solvent is ethanol, methyl alcohol or acetone.
21. preparation method as claimed in claim 9 is characterized in that, said resin bed is under 20～180 ℃ temperature, to be incubated 30～450 minutes to solidify to form resin bed.
22. preparation method as claimed in claim 9 is characterized in that, the thickness of said micro nano structure layer is less than or equal to 600nm.
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