CN103509396B - The preparation method of hydrophobic antimicrobial coating - Google Patents
The preparation method of hydrophobic antimicrobial coating Download PDFInfo
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- CN103509396B CN103509396B CN201310420130.6A CN201310420130A CN103509396B CN 103509396 B CN103509396 B CN 103509396B CN 201310420130 A CN201310420130 A CN 201310420130A CN 103509396 B CN103509396 B CN 103509396B
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- silver
- coating
- hydrophobic
- colored
- dispersion liquid
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- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 35
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000007970 homogeneous dispersion Substances 0.000 claims abstract description 4
- 238000007711 solidification Methods 0.000 claims abstract description 4
- 230000008023 solidification Effects 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 6
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 235000001968 nicotinic acid Nutrition 0.000 abstract description 2
- -1 silver ions Chemical class 0.000 abstract description 2
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 4
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 4
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 210000001595 mastoid Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
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- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to the preparation of antimicrobial coating, aim to provide a kind of preparation method of hydrophobic antimicrobial coating.The method comprises: adopt modified fluorin resin at cleaned substrates surface coatings, prepare hydrophobic coating; Before this hydrophobic coating surface drying, hydrophobically modified hollow silica is carried silver-colored microballoon homogeneous dispersion and be applied to its surface, after solidification, obtain hydrophobic antimicrobial coating.The present invention is based on bionics techniques principle, utilize unloaded silver-colored microballoon in mesoporous silicon oxide to be partially submerged in fluorine-containing organic membrane, on the one hand by the coating surface structure that structure micro-nano is coarse, strengthen coating hydrophobic performance further; Utilize on the other hand the structure of unloaded silver-colored microballoon uniqueness in this, carried the long-term slow releasing silver ions of mesoporous passage of silver-colored microsphere surface by hollow silica, play the effect of durable antibiotic, thus realize the integrated of coating sustained-released antibacterial and super hydrophobic functional.
Description
Technical field
The present invention relates to the preparation of antimicrobial coating, particularly a kind of preparation method of hydrophobic antimicrobial coating.
Background technology
Be in the body surface often easy grow mold in wet environment for a long time, body surface done hydrophobization process and can effectively avoid moisture, dirt in body surface enrichment, reduce mould growing at body surface.At present, applying more is low surface energy fluorine material, and generally speaking monomer Oil repellent is higher, and hydrophobic performance is better, but price also can significantly improve.By research lotus leaf automatically cleaning phenomenon, Univ Bonn Germany researchist finds that lotus leaf top layer grows nano level wax crystalline substance, make lotus leaf surface hydrophobic, the micron mastoid process etc. of lotus leaf surface forms micro-roughened surface and strengthens its hydrophobicity further simultaneously, make dirt not easily at its surface enrichment, give its self-cleaning function.In addition, the hydrophobic coating function of current application is general comparatively single, although some researchs add antibacterial components in hydrophobic coating, realizes the integrated of hydrophobic function and antibacterial, but be in the easy a large amount of stripping of surperficial antibacterial active constituents and run off, causing coating Durability of antimicrobial effect to reduce.Therefore, how by surface structure design structure one hydrophobic, sustained-release antibacterial coating system efficiently, become and be rich in a challenging development.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of preparation method of hydrophobic antimicrobial coating.
For technical solution problem, the invention provides a kind of preparation method of hydrophobic antimicrobial coating, comprise the steps:
(1) adopt solid content be the modified fluorin resin of 5% ~ 40% at cleaned substrates surface coatings, prepare hydrophobic coating;
(2) before this hydrophobic coating surface drying, be that the hydrophobically modified hollow silica of 8 ~ 40g/L carries silver-colored microballoon homogeneous dispersion and is applied to its surface by mass concentration, after solidification, obtain hydrophobic antimicrobial coating;
Described hydrophobically modified hollow silica carries silver-colored microballoon dispersion liquid and prepares according to the following procedure:
A, polystyrene microsphere is added mass percentage concentration is in the vitriol oil of 98%, and polystyrene in concentrated sulfuric acid mass concentration is 20g/L; Stir 6h at 50 DEG C, centrifugal, deionized water wash 4 times, is then re-dispersed in dehydrated alcohol, obtains the sulfonated polystyrene dispersion liquid that mass concentration is 5g/L repeatedly;
B, in above-mentioned sulfonated polystyrene dispersion liquid, the mass concentration adding quality same with this dispersion liquid is the tin protochloride aqueous solution of 5g/L; Stirred at ambient temperature 30min, centrifugal, washing after, join in the silver ammino solution of the 0.1mol/L being dissolved with Seignette salt, Seignette salt: silver-colored ammonium ion: tin protochloride mol ratio is 10: 5: 1; Stirred at ambient temperature 1h, adds Virahol in the resulting mixture, and the volume ratio of Virahol and mixture is 2: 3, obtains carrying silver-colored polystyrene complex microsphere dispersion liquid;
C, in above-mentioned year silver-colored polystyrene complex microsphere dispersion liquid, add tetraethoxy and mass percentage concentration is the ammoniacal liquor of 28%, Virahol in mixed solution: ammoniacal liquor: the volume ratio of tetraethoxy is 60: 3: 5; Stirred at ambient temperature 24h, products therefrom through centrifugal, washing after, at 550 DEG C, calcine 2h, namely obtain hollow silica carry silver-colored microballoon;
D, this hollow silica carried silver-colored microballoon and to be distributed to identical type in step (1) and solid content is in the modified fluorin resin of 2%, after ageing 8h, obtain hydrophobically modified hollow silica and carry silver-colored microballoon dispersion liquid.
In the present invention, modified fluorin resin described in step (1) is the one in acrylic acid modified fluoro-resin or organic-silicon-modified fluoro-resin.
In the present invention, described in step (1), the preparation method of hydrophobic coating and hydrophobic antimicrobial coating is spin-coating method or spraying method.
In the present invention, described cleaned substrates be through water cleaning and dry surface without the pottery of obvious stain, concrete, paint film any one.
Compared with existing technology of preparing, the invention has the beneficial effects as follows:
The present invention is based on bionics techniques principle, utilize unloaded silver-colored microballoon in mesoporous silicon oxide to be partially submerged in fluorine-containing organic membrane, on the one hand by the coating surface structure that structure micro-nano is coarse, strengthen coating hydrophobic performance further; Utilize on the other hand the structure of unloaded silver-colored microballoon uniqueness in this, carried the long-term slow releasing silver ions of mesoporous passage of silver-colored microsphere surface by hollow silica, play the effect of durable antibiotic, thus realize the integrated of coating sustained-released antibacterial and super hydrophobic functional.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph (apparent form photo) of unloaded silver-colored microballoon in mesoporous silicon oxide;
Fig. 2 is the stereoscan photograph (be microballoon spherical shell internal pictures, lighter colored particles is the nano-Ag particles of load in spherical shell inside) of unloaded silver-colored microballoon in mesoporous silicon oxide;
Fig. 3 is the stereoscan photograph of hydrophobic antimicrobial coatingsurface;
Fig. 4 is contact angle contrast photo (water droplet at the contact angle of modified fluorin resin hydrophobic coating surface be 112.0 °) of different coating to water;
Fig. 5 is for different coating is to the contact angle contrast photo (contact angle of water droplet hydrophobic antimicrobial coatingsurface prepared by the identical modified fluorin resin of employing is 150.4 °) of water.
Embodiment
Below by way of example, the present invention is further described.
The preparation method of hydrophobic antimicrobial coating provided by the invention, comprises the steps:
(1) adopt solid content be the modified fluorin resin of 5% ~ 40% at cleaned substrates surface coatings, prepare hydrophobic coating;
(2) before this hydrophobic coating surface drying, be that the hydrophobically modified hollow silica of 8 ~ 40g/L carries silver-colored microballoon homogeneous dispersion and is applied to its surface by mass concentration, after solidification, obtain hydrophobic antimicrobial coating;
Described hydrophobically modified hollow silica carries silver-colored microballoon dispersion liquid and prepares according to the following procedure:
A, polystyrene microsphere is added mass percentage concentration is in the vitriol oil of 98%, and polystyrene in concentrated sulfuric acid mass concentration is 20g/L; Stir 6h at 50 DEG C, centrifugal, deionized water wash 4 times, is then re-dispersed in dehydrated alcohol, obtains the sulfonated polystyrene dispersion liquid that mass concentration is 5g/L repeatedly;
B, in above-mentioned sulfonated polystyrene dispersion liquid, the mass concentration adding quality same with this dispersion liquid is the tin protochloride aqueous solution of 5g/L; Stirred at ambient temperature 30min, centrifugal, washing after, join in the silver ammino solution of the 0.1mol/L being dissolved with Seignette salt, Seignette salt: silver-colored ammonium ion: tin protochloride mol ratio is 10: 5: 1; Stirred at ambient temperature 1h, adds Virahol in the resulting mixture, and the volume ratio of Virahol and mixture is 2: 3, obtains carrying silver-colored polystyrene complex microsphere dispersion liquid;
C, in above-mentioned year silver-colored polystyrene complex microsphere dispersion liquid, add tetraethoxy and mass percentage concentration is the ammoniacal liquor of 28%, Virahol in mixed solution: ammoniacal liquor: the volume ratio of tetraethoxy is 60: 3: 5; Stirred at ambient temperature 24h, products therefrom through centrifugal, washing after, at 550 DEG C, calcine 2h, namely obtain hollow silica carry silver-colored microballoon;
D, this hollow silica carried silver-colored microballoon and to be distributed to identical type in step (1) and solid content is in the modified fluorin resin of 2%, after ageing 8h, obtain hydrophobically modified hollow silica and carry silver-colored microballoon dispersion liquid.
In each embodiment, except the difference to some extent of testing data in following table, all the other testing datas are all identical.
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (3)
1. a preparation method for hydrophobic antimicrobial coating, is characterized in that, comprises the steps:
(1) adopt solid content be the modified fluorin resin of 5% ~ 40% at cleaned substrates surface coatings, prepare hydrophobic coating;
(2) before this hydrophobic coating surface drying, be that the hydrophobically modified hollow silica of 8 ~ 40g/L carries silver-colored microballoon homogeneous dispersion and is applied to its surface by mass concentration, after solidification, obtain hydrophobic antimicrobial coating;
Described in step (1), the preparation method of hydrophobic coating and hydrophobic antimicrobial coating is spin-coating method or spraying method;
Described hydrophobically modified hollow silica carries silver-colored microballoon dispersion liquid and prepares according to the following procedure:
A, polystyrene microsphere is added mass percentage concentration is in the vitriol oil of 98%, and polystyrene in concentrated sulfuric acid mass concentration is 20g/L; Stir 6h at 50 DEG C, centrifugal, deionized water wash 4 times, is then re-dispersed in dehydrated alcohol, obtains the sulfonated polystyrene dispersion liquid that mass concentration is 5g/L repeatedly;
B, in above-mentioned sulfonated polystyrene dispersion liquid, the mass concentration adding quality same with this dispersion liquid is the tin protochloride aqueous solution of 5g/L; Stirred at ambient temperature 30min, centrifugal, washing after, join in the silver ammino solution of the 0.1mol/L being dissolved with Seignette salt, Seignette salt: silver-colored ammonium ion: tin protochloride mol ratio is 10: 5: 1; Stirred at ambient temperature 1h, adds Virahol in the resulting mixture, and the volume ratio of Virahol and mixture is 2: 3, obtains carrying silver-colored polystyrene complex microsphere dispersion liquid;
C, in above-mentioned year silver-colored polystyrene complex microsphere dispersion liquid, add tetraethoxy and mass percentage concentration is the ammoniacal liquor of 28%, Virahol in mixed solution: ammoniacal liquor: the volume ratio of tetraethoxy is 60: 3: 5; Stirred at ambient temperature 24h, products therefrom through centrifugal, washing after, at 550 DEG C, calcine 2h, namely obtain hollow silica carry silver-colored microballoon;
D, this hollow silica carried silver-colored microballoon and to be distributed to identical type in step (1) and solid content is in the modified fluorin resin of 2%, after ageing 8h, obtain hydrophobically modified hollow silica and carry silver-colored microballoon dispersion liquid.
2. method according to claim 1, is characterized in that, modified fluorin resin described in step (1) is acrylic acid modified fluoro-resin or organic-silicon-modified fluoro-resin.
3. method according to claim 1, is characterized in that, described cleaned substrates be through water cleaning and dry surface without the pottery of obvious stain, concrete, paint film any one.
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| CN201310420130.6A CN103509396B (en) | 2013-09-15 | 2013-09-15 | The preparation method of hydrophobic antimicrobial coating |
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| CN201310420130.6A CN103509396B (en) | 2013-09-15 | 2013-09-15 | The preparation method of hydrophobic antimicrobial coating |
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| CN103509396B true CN103509396B (en) | 2016-03-16 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861657B (en) * | 2014-02-24 | 2015-07-08 | 浙江大学 | Preparation method of nano-silver loaded porous silicon dioxide |
| CN103894122B (en) * | 2014-04-14 | 2015-09-16 | 浙江大学 | The preparation method of soluble type drug loading microcapsules |
| CN104310795B (en) * | 2014-09-29 | 2016-11-02 | 北京师范大学 | A kind of preparation method of substrate surface antimicrobial coating |
| CN105921130A (en) * | 2016-05-25 | 2016-09-07 | 厦门建霖工业有限公司 | Slow-release antibacterial adsorption material for drinking water treatment and preparation method of material |
| CN106436284B (en) * | 2016-09-27 | 2018-10-12 | 天津傲卓菲科技有限公司 | A kind of simple self-spraying tank of rapid build super-double-hydrophobic surface |
| TW202037683A (en) * | 2019-04-02 | 2020-10-16 | 新福光塗裝工程股份有限公司 | Antibacterial coating and coating method which includes antibacterial particles that are all located near a surface of the paint with excellent abrasion resistance and adhesion performance |
| CN110592959B (en) * | 2019-08-27 | 2020-12-08 | 玉环市几偶孵化器有限公司 | Self-cleaning textile material for automotive interior and preparation method thereof |
| CN115121193B (en) * | 2022-07-25 | 2023-08-08 | 西安理工大学 | Preparation method of positively charged AgO@MgO hollow composite microspheres |
| CN116463024A (en) * | 2023-05-29 | 2023-07-21 | 杭州老板电器股份有限公司 | Hydrophobic oleophobic antibacterial film layer and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242511A (en) * | 1990-02-23 | 1993-09-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Copper alloy compositions |
| CN101058687A (en) * | 2007-02-18 | 2007-10-24 | 张弛一智 | Enhancement self-cleaning antibiotic low surface energy coat capable of being monitored |
| CN102669178A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Method for preparing sustained-release silver-based antibacterial agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3316861B2 (en) * | 1991-11-06 | 2002-08-19 | 松下電器産業株式会社 | Antibacterial treatment material and its manufacturing method |
| JPH10179403A (en) * | 1996-12-20 | 1998-07-07 | Nikkei Prod:Kk | Cooking vessel and production of its parts |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242511A (en) * | 1990-02-23 | 1993-09-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Copper alloy compositions |
| CN101058687A (en) * | 2007-02-18 | 2007-10-24 | 张弛一智 | Enhancement self-cleaning antibiotic low surface energy coat capable of being monitored |
| CN102669178A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Method for preparing sustained-release silver-based antibacterial agent |
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