CN103509396A - Preparation method of novel hydrophobic anti-microbial coating - Google Patents
Preparation method of novel hydrophobic anti-microbial coating Download PDFInfo
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- CN103509396A CN103509396A CN201310420130.6A CN201310420130A CN103509396A CN 103509396 A CN103509396 A CN 103509396A CN 201310420130 A CN201310420130 A CN 201310420130A CN 103509396 A CN103509396 A CN 103509396A
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Abstract
The invention relates to preparation of an anti-microbial coating, and aims to provide a preparation method of a novel hydrophobic anti-microbial coating. The method comprises the following steps: adopting modified fluororesin to film the surface of a clean substrate to prepare a hydrophobic coating; before the hydrophobic coating surface is dried, uniformly coating hydrophobically modified silicon dioxide hollow silver-loaded microspheres on the surface, and after solidifying, obtaining the novel hydrophobic anti-microbial coating. Based on the principle of a biomimetic technology, the method is to embed the mesoporous silica hollow silver-loaded microsphere part in the fluorine-containing organic membrane, on one hand further increases the hydrophobic property of the coating through constructing the nanometer rough coating surface structure, and on the other hand serves a long-lasting antimicrobial function by virtue of the unique structure of the hollow silver-loaded microspheres to slowly release silver ions through the mesoporous channels on the silicon dioxide hollow silver-loaded microsphere surface, so as to achieve integration of the slowly-releasing antimicrobial function and the super-hydrophobic function of the coating.
Description
Technical field
The present invention relates to the preparation of antimicrobial coating, particularly a kind of preparation method of new hydrophobic antimicrobial coating.
Background technology
Long-term body surface in wet environment is easy grow mold often, body surface is done to hydrophobization processing and can effectively avoid moisture, dirt in body surface enrichment, reduces mould growing at body surface.At present, applying more is low surface energy fluorine material, and generally speaking monomer fluorine content is higher, and hydrophobic performance is better, but price also can significantly improve.The researchist of Univ Bonn Germany finds that by research lotus leaf automatically cleaning phenomenon the lotus leaf top layer nano level wax of growing is brilliant, make lotus leaf surface hydrophobic, the micron mastoid process of while lotus leaf surface etc. forms micro-rough surface and further strengthens its hydrophobicity, make dirt be difficult for, at its surface enrichment, giving its self-cleaning function.In addition, the hydrophobic coating function of application is generally comparatively single at present, although antibacterial components is added in some researchs in hydrophobic coating, realizes the integrated of hydrophobic function and antibacterial, but in the easily a large amount of strippings of surperficial anti-microbial activity component, run off, cause coating Durability of antimicrobial effect to reduce.Therefore, how by surface structure design, to construct a kind of hydrophobic, slowly-releasing antimicrobial 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, and a kind of preparation method of new hydrophobic antimicrobial coating is provided.
For technical solution problem, the invention provides a kind of preparation method of new hydrophobic antimicrobial coating, comprise the steps:
(1) adopt the modified fluorin resin that solid content is 5%～40% to film at clean substrate surface, prepare hydrophobic coating;
(2) before this hydrophobic coating surface drying, in the hydrophobically modified silicon-dioxide that is 8～40g/L by mass concentration, unloaded silver-colored microballoon dispersion liquid is evenly applied to its surface, after solidifying, obtains new hydrophobic antimicrobial coating;
In described hydrophobically modified silicon-dioxide, unloaded silver-colored microballoon dispersion liquid prepares according to the following procedure:
A, polystyrene microsphere is added to mass percentage concentration is that in 98% the vitriol oil, polystyrene mass concentration in the vitriol oil is 20g/L; At 50 ℃, stir 6h, centrifugal, deionized water wash is 4 times repeatedly, is then re-dispersed in dehydrated alcohol, and obtaining mass concentration is the sulfonated polystyrene dispersion liquid of 5g/L;
B, in above-mentioned sulfonated polystyrene dispersion liquid, add the tin protochloride aqueous solution that the mass concentration with the same quality of this dispersion liquid is 5g/L; Under room temperature, stir 30min, centrifugal, washing after, join in the silver ammino solution of the 0.1mol/L that is dissolved with Seignette salt Seignette salt: silver-colored ammonium ion: tin protochloride mol ratio is 10: 5: 1; Under room temperature, stir 1h, in gained mixture, add Virahol, 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, adding tetraethoxy and mass percentage concentration is 28% ammoniacal liquor, Virahol in mixed solution: ammoniacal liquor: the volume ratio of tetraethoxy is 60: 3: 5; Under room temperature, stir 24h, products therefrom through centrifugal, washing after, at 550 ℃, calcine 2h, obtain unloaded silver-colored microballoon in silicon-dioxide;
D, by unloaded silver-colored microballoon in this silicon-dioxide be distributed to step (1) in identical type and the solid content modified fluorin resin that is 2%, after ageing 8h, obtain unloaded silver-colored microballoon dispersion liquid in hydrophobically modified silicon-dioxide.
In the present invention, modified fluorin resin described in step (1) is a kind of 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 new hydrophobic antimicrobial coating is spin-coating method or spraying method.
In the present invention, described clean base material be through water clean and dry surface without any one of the pottery of obvious stain, concrete, paint film.
Compare 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, by the coarse coating surface structure of structure micro-nano, further strengthen coating hydrophobic performance on the one hand; Utilize on the other hand the structure of unloaded silver-colored microballoon uniqueness in this, the long-term silver ions that slowly discharges of mesoporous passage by unloaded silver-colored microsphere surface in silicon-dioxide, plays the effect of durable antibiotic, thereby realizes the integrated of coating sustained-released antibiotic and super hydrophobic functional.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph (apparent pattern photo) of unloaded silver-colored microballoon in mesoporous silicon oxide;
Fig. 2 is the stereoscan photograph (be the inner photo of microballoon spherical shell, lighter colored particles is the nano-Ag particles that loads on spherical shell inside) of unloaded silver-colored microballoon in mesoporous silicon oxide;
Fig. 3 is the stereoscan photograph on new hydrophobic antimicrobial coating surface;
Fig. 4 is the contact angle contrast photo (water droplet contact angle on modified fluorin resin hydrophobic coating surface be 112.0 °) of different coating to water;
Fig. 5 is the contact angle contrast photo (water droplet at the contact angle on employing identical modified fluorin resin prepared new hydrophobic antimicrobial coating surface be 150.4 °) of different coating to water.
Embodiment
Below by example, the present invention is further described.
The preparation method of new hydrophobic antimicrobial coating provided by the invention, comprises the steps:
(1) adopt the modified fluorin resin that solid content is 5%～40% to film at clean substrate surface, prepare hydrophobic coating;
(2) before this hydrophobic coating surface drying, in the hydrophobically modified silicon-dioxide that is 8～40g/L by mass concentration, unloaded silver-colored microballoon dispersion liquid is evenly applied to its surface, after solidifying, obtains new hydrophobic antimicrobial coating;
In described hydrophobically modified silicon-dioxide, unloaded silver-colored microballoon dispersion liquid prepares according to the following procedure:
A, polystyrene microsphere is added to mass percentage concentration is that in 98% the vitriol oil, polystyrene mass concentration in the vitriol oil is 20g/L; At 50 ℃, stir 6h, centrifugal, deionized water wash is 4 times repeatedly, is then re-dispersed in dehydrated alcohol, and obtaining mass concentration is the sulfonated polystyrene dispersion liquid of 5g/L;
B, in above-mentioned sulfonated polystyrene dispersion liquid, add the tin protochloride aqueous solution that the mass concentration with the same quality of this dispersion liquid is 5g/L; Under room temperature, stir 30min, centrifugal, washing after, join in the silver ammino solution of the 0.1mol/L that is dissolved with Seignette salt Seignette salt: silver-colored ammonium ion: tin protochloride mol ratio is 10: 5: 1; Under room temperature, stir 1h, in gained mixture, add Virahol, 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, adding tetraethoxy and mass percentage concentration is 28% ammoniacal liquor, Virahol in mixed solution: ammoniacal liquor: the volume ratio of tetraethoxy is 60: 3: 5; Under room temperature, stir 24h, products therefrom through centrifugal, washing after, at 550 ℃, calcine 2h, obtain unloaded silver-colored microballoon in silicon-dioxide;
D, by unloaded silver-colored microballoon in this silicon-dioxide be distributed to step (1) in identical type and the solid content modified fluorin resin that is 2%, after ageing 8h, obtain unloaded silver-colored microballoon dispersion liquid in hydrophobically modified silicon-dioxide.
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, what more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above examples of implementation, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. a preparation method for new hydrophobic antimicrobial coating, is characterized in that, comprises the steps:
(1) adopt the modified fluorin resin that solid content is 5%～40% to film at clean substrate surface, prepare hydrophobic coating;
(2) before this hydrophobic coating surface drying, in the hydrophobically modified silicon-dioxide that is 8～40g/L by mass concentration, unloaded silver-colored microballoon dispersion liquid is evenly applied to its surface, after solidifying, obtains new hydrophobic antimicrobial coating;
In described hydrophobically modified silicon-dioxide, unloaded silver-colored microballoon dispersion liquid prepares according to the following procedure:
A, polystyrene microsphere is added to mass percentage concentration is that in 98% the vitriol oil, polystyrene mass concentration in the vitriol oil is 20g/L; At 50 ℃, stir 6h, centrifugal, deionized water wash is 4 times repeatedly, is then re-dispersed in dehydrated alcohol, and obtaining mass concentration is the sulfonated polystyrene dispersion liquid of 5g/L;
B, in above-mentioned sulfonated polystyrene dispersion liquid, add the tin protochloride aqueous solution that the mass concentration with the same quality of this dispersion liquid is 5g/L; Under room temperature, stir 30min, centrifugal, washing after, join in the silver ammino solution of the 0.1mol/L that is dissolved with Seignette salt Seignette salt: silver-colored ammonium ion: tin protochloride mol ratio is 10: 5: 1; Under room temperature, stir 1h, in gained mixture, add Virahol, 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, adding tetraethoxy and mass percentage concentration is 28% ammoniacal liquor, Virahol in mixed solution: ammoniacal liquor: the volume ratio of tetraethoxy is 60: 3: 5; Under room temperature, stir 24h, products therefrom through centrifugal, washing after, at 550 ℃, calcine 2h, obtain unloaded silver-colored microballoon in silicon-dioxide;
D, by unloaded silver-colored microballoon in this silicon-dioxide be distributed to step (1) in identical type and the solid content modified fluorin resin that is 2%, after ageing 8h, obtain unloaded silver-colored microballoon dispersion liquid in hydrophobically modified silicon-dioxide.
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 in step (1), the preparation method of hydrophobic coating and new hydrophobic antimicrobial coating is spin-coating method or spraying method.
4. method according to claim 1, is characterized in that, described clean base material be through water clean and dry surface without any one of the pottery of obvious stain, concrete, paint film.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861657A (en) * | 2014-02-24 | 2014-06-18 | 浙江大学 | Preparation method of nano-silver loaded porous silicon dioxide |
| CN103894122A (en) * | 2014-04-14 | 2014-07-02 | 浙江大学 | Preparation method of soluble medicine loaded microcapsule |
| CN104310795A (en) * | 2014-09-29 | 2015-01-28 | 北京师范大学 | Preparation method of antimicrobial coating on substrate surface |
| 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 |
| CN106436284A (en) * | 2016-09-27 | 2017-02-22 | 天津傲卓菲科技有限公司 | Simple automatic spray tank with function of quickly constructing super-amphiphobic surfaces |
| CN110592959A (en) * | 2019-08-27 | 2019-12-20 | 台州市旭泓服饰有限公司 | Self-cleaning textile material for automotive interior and preparation method thereof |
| CN111793378A (en) * | 2019-04-02 | 2020-10-20 | 新福光涂装工程股份有限公司 | Antibacterial coating and coating method thereof |
| CN115121193A (en) * | 2022-07-25 | 2022-09-30 | 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 |
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| US5242511A (en) * | 1990-02-23 | 1993-09-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Copper alloy compositions |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861657A (en) * | 2014-02-24 | 2014-06-18 | 浙江大学 | Preparation method of nano-silver loaded porous silicon dioxide |
| 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 |
| CN103894122A (en) * | 2014-04-14 | 2014-07-02 | 浙江大学 | Preparation method of soluble medicine loaded microcapsule |
| CN104310795B (en) * | 2014-09-29 | 2016-11-02 | 北京师范大学 | A kind of preparation method of substrate surface antimicrobial coating |
| CN104310795A (en) * | 2014-09-29 | 2015-01-28 | 北京师范大学 | Preparation method of antimicrobial coating on substrate surface |
| 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 |
| CN106436284A (en) * | 2016-09-27 | 2017-02-22 | 天津傲卓菲科技有限公司 | Simple automatic spray tank with function of quickly constructing super-amphiphobic surfaces |
| 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 |
| CN111793378A (en) * | 2019-04-02 | 2020-10-20 | 新福光涂装工程股份有限公司 | Antibacterial coating and coating method thereof |
| CN110592959A (en) * | 2019-08-27 | 2019-12-20 | 台州市旭泓服饰有限公司 | Self-cleaning textile material for automotive interior and preparation method thereof |
| CN115121193A (en) * | 2022-07-25 | 2022-09-30 | 西安理工大学 | Preparation method of positively charged AgO @ MgO hollow composite microspheres |
| 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 |
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