CN104098969A - Coating with low surface energy and high deicing easiness as well as preparation method of coating - Google Patents
Coating with low surface energy and high deicing easiness as well as preparation method of coating Download PDFInfo
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- CN104098969A CN104098969A CN201410355116.7A CN201410355116A CN104098969A CN 104098969 A CN104098969 A CN 104098969A CN 201410355116 A CN201410355116 A CN 201410355116A CN 104098969 A CN104098969 A CN 104098969A
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Abstract
The invention provides a coating with low surface energy and high deicing easiness. The coating adopts fluorine-modified acrylic resin which is excellent in low surface energy and weatherability as a base stock, adopts nanoscale hydrophobic silicon dioxide as a filling material, and utilizes the tail end needle-shaped structure of polyacrylonitrile nanometer fiber to ensure that the microcosmic surface of the coating has certain strength and roughness; the lotus effect is realized on the surface of the coating to reduce the contact area between water and the surface of the coating. Therefore, under the premise that water droplets cannot adhere onto the coating, the adhering strength of ice on the coating is also reduced greatly, that is, the hydrophobicity and the deicing easiness are high.
Description
[technical field]
The present invention relates to a kind of coating and preparation method thereof, be specifically related to coating of the easy deicing of a kind of low surface energy and preparation method thereof.
[background technology]
Known, along with the fast development of modern industry, the reliability of supply network has been proposed to more and more higher requirement, wherein icing and accumulated snow are one of natural disasteies of serious threat power system security, in Russia, Canada, the U.S., Japan, Britain, China the north and Midwest cold zone, all there is serious ice and snow disaster in south China even in recent years, the icing of electric power pylon causes circuit to damage to local people's production and life having brought great inconvenience, and cause serious financial loss, therefore effectively avoid and prevent the harm that ice damage causes transmission of electricity electric power pylon, it is the problem that electric power enterprise must be faced.At present, in order to overcome above-mentioned technical problem, deicing mode both domestic and external is mainly that (1) adopts suitable deicing machinery to carry out deicing; (2) by substrate surface is coated with and spreads anti-icing agent, reduce freezing point; (3) by substrate surface is heated to deicing etc.Aforesaid method all needs very large manpower and material resources, and can not play the effect of prevention in advance.For effectively reducing the covering of ice and snow and reducing ice and snow sticking power in transmission tower, effective method applies ice-covering-proof coating protection exactly.
Existing anti-icing paint is mainly made up of modification acrylate class, silicone based and fluoropolymer etc. in the market.Boeing Co. adopts organosilicon hydrophobic system, uses containing the compound of isocyanate groups silicone resin is carried out to modification, obtains the good anti-icing paint of metal base sticking power; Microphase Coatings company of the U.S. adopts the coating of silicone resin and the composite formation interpenetrating(polymer)networks of epoxy resin, and these series product are applied.Nippon Paint Co., Ltd. (Nippon Paint) had once successfully developed in 2003 and can form the coating depositing by Anti-ice-and-snow, they add the additives such as silica pellet in organosilicon-acrylic copolymer resin, make film have the water contact angle of approximately 160 °; The domestic anti-icing paint that mainly contains Beijing will Sheng Weihua chemistry painting industry company limited, mainly forms by many blocks inorganic-organic interpenetrating net polymer (IPN) base-material of alternative arrangement with through the high-activity nano Anti-ice-and-snow agent of surface modification treatment; Within 2008, Inst. of Marine Chemical Engineering has synthesized fluorine silicon ultra-low surface energy acrylic resin, and has developed the coating with excellent hydrophobic nature, and it is anti-freeze that application direction is mainly aircraft surfaces.
Find through retrieval, Chinese patent, publication number is CN102260444A and Chinese patent, publication number is that the disclosed ice-covering-proof coating of CN102146249 A all has good hydrophobic type, reduce the adsorption effect of coatingsurface to the globule, thereby reach ice-covering-proof object, but disclosed existing anti-icing paint mainly taking reduce rainwater and ice and snow at the resident hydrophobic performance of coatingsurface as main, reduce adhering to of electric power pylon surface ice and snow thereby reach, but can not fundamentally stop the formation of ice, once electric power pylon surface forms after snow and ice cover, still needing to spend a large amount of man power and materials removes, and it is very large to remove difficulty.
[summary of the invention]
In order to overcome the deficiency existing in background technology, the invention provides coating of the easy deicing of a kind of low surface energy and preparation method thereof, the present invention forms lotus leaf effect at coatingsurface, reduce the contact area of water and coatingsurface, in making water droplet be difficult to adhere in coating, the adhesion strength of ice in coating also reduces greatly, thereby realizes high hydrophobicity and easily deicing.
For realizing goal of the invention as above, the present invention adopts technical scheme as described below:
A coating for the easy deicing of low surface energy, described coating comprises first component and second component, described first component comprises following composition by mass percentage:
Fluorin modified crylic acid resin 70～80%;
Hydrophobic SiO
22～4%;
Microcrystal 6～10%;
Color stuffing 8～15%;
Auxiliary agent 2～3%;
Described second component is isocyanate trimerization body;
The ratio of described first component and second component is 10～15:1.
The coating of the described easy deicing of low surface energy, the solid content of described fluorin modified crylic acid resin base-material is 40～80%.
The coating of the described easy deicing of low surface energy, described hydrophobic SiO
2the SiO being replaced by silane group for surface hydroxyl 50～80%
2.
The coating of the described easy deicing of low surface energy, described microcrystal is the whisker with acicular structure.
The coating of the described easy deicing of low surface energy, the pigment in described color stuffing is any one in carbon black or phthalocyanine blue or iron oxide yellow or titanium dioxide, filler is one or both in talcum powder or sericite in powder or ground barium sulfate.
The coating of the described easy deicing of low surface energy, described auxiliary agent is any one in BYK series defoamer or flow agent or dispersion agent or fluorine auxiliary agent.
The coating of the described easy deicing of low surface energy, described isocyanate trimerization body is isocyanic ester " HDI " tripolymer N3390.
A preparation method for the coating of the easy deicing of low surface energy, described preparation method specifically comprises the steps:
One, preparation first component:
By the fluorin modified crylic acid resin, the hydrophobic SiO that accurately weigh
2, microcrystal and auxiliary agent put into charging basket, with high speed dispersor stirring at low speed 10～15min, after being uniformly dispersed, add color stuffing according to many principles after heavy after first light, first few again, then high-speed stirring 30～60min, after being uniformly dispersed, grind again 2～3h to coating fineness below 40 μ m, then detect viscosity, detect after qualified and obtain first component through filtration, discharging, packaging;
Two, prepare coating:
Connect step, the first component that the first step is obtained and second component are mixed by the proportioning of 10～15:1, after employing stirrer stirs, can obtain required coating.
The preparation method of the coating of the described easy deicing of low surface energy, the speed of described high-speed stirring is 1500～2000r/min.
The preparation method of the coating of the described easy deicing of low surface energy, the speed of described stirring at low speed is 400～800 r/min.
Adopt technical scheme as above, the present invention has superiority as described below:
Coating of the easy deicing of a kind of low surface energy of the present invention and preparation method thereof, the fluorin modified crylic acid resin that the present invention's employing has excellent low surface energy and weather resistance is base-material, taking nano level water drain silica as filler, utilize the end acicular structure of polyacrylonitrile nanofiber, give intensity that coating is certain and the microcosmic surface of certain roughness, form lotus leaf effect at coatingsurface, reduce the contact area of water and coatingsurface, in making water droplet be difficult to adhere in coating, the adhesion strength of ice in coating also reduces greatly, thereby realize high hydrophobicity and easily deicing.
[embodiment]
Can explain in more detail the present invention by the following examples, the present invention is not limited to the following examples:
The coating of the easy deicing of a kind of low surface energy of the present invention, described coating comprises first component and second component, described first component comprises following composition by mass percentage:
Fluorin modified crylic acid resin 70～80%; Hydrophobic SiO
22～4%;
Microcrystal 6～10%; Color stuffing 8～15%; Auxiliary agent 2～3%;
Described second component is isocyanate trimerization body, and described isocyanate trimerization body is isocyanic ester " HDI " tripolymer N3390;
The ratio of described first component and second component is 10～15:1.
The solid content of wherein said fluorin modified crylic acid resin base-material is 40～80%, and resin solid content refers under certain temperature, and after solvent evaporated, remaining weight resin accounts for the percentage ratio of former gross weight.
Wherein said hydrophobic SiO
2the SiO being replaced by silane group for surface hydroxyl 50～80%
2.
Wherein said microcrystal is the whisker with acicular structure.
Pigment in wherein said color stuffing is any one in carbon black or phthalocyanine blue or iron oxide yellow or titanium dioxide, and filler is one or both in talcum powder or sericite in powder or ground barium sulfate.
Wherein said auxiliary agent is any one in BYK series defoamer or flow agent or dispersion agent or fluorine auxiliary agent.
A preparation method for the coating of the easy deicing of low surface energy, described preparation method specifically comprises the steps:
One, preparation first component:
By the fluorin modified crylic acid resin, the hydrophobic SiO that accurately weigh
2, microcrystal and auxiliary agent put into charging basket, with high speed dispersor stirring at low speed 10～15min, the speed of described stirring at low speed is 400～800 r/min, after being uniformly dispersed, add color stuffing according to many principles after heavy after first light, first few again, then high-speed stirring 30～60min, the speed of described high-speed stirring is 1500～2000r/min, after being uniformly dispersed, grind again 2～3h to coating fineness below 40 μ m, then detect viscosity, detect after qualified and obtain first component through filtration, discharging, packaging;
Two, prepare coating:
Connect step, the first component that the first step is obtained and second component are mixed by the proportioning of 10～15:1, after employing electric blender stirs, can obtain required coating.
The key technical indexes of product of the present invention is as shown in the table:
| Sequence number | Project | Technical indicator | The method of inspection |
| 1 | Snappiness, mm | 2 | GB/T1731-1993 |
| 2 | Shock strength, cm | 50 | GB/T1732-1993 |
| 3 | Sticking power, level | 1 | GB/T 9286-1998 |
| 4 | Salt spray resistance, 1000h | Paint film is non-foaming, do not come off, non-corroding | GB/T 1771-2007 |
| 5 | Wet-heat resisting, 1000h | 47±1℃，1000h | GB/T 1740-2007 |
| 6 | Resistance to artificial accelerated aging, 1000h | 0 grade of efflorescence, 1 grade of variable color, ftractures 0 grade | GB/T 1865-2009 |
| 7 | To fresh water contact angle, θ | ≥120° | ASTMD 724-2003 |
| 8 | Resistance to artificial contamination's property | ≥70% | MIL-PRF-85285D |
| 9 | Easily deicing | ≤1×10 4N | Coatingsurface ice cube diameter is 6cm, vertically drop-down |
The present invention is applied to the two component finish paint coating of electric power pylon surface low surface energy fluorin modified crylic acid, mainly adopts two component spray (Airless spraying, aerial spraying all can), per pass application build 60 μ m, suggestion application twice.Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between embodiment.
Embodiment mono-:
First, second component proportion is 10:1, and wherein second component is isocyanic ester " HDI " tripolymer N3390; The table composed as follows of first component:
| Starting material | Formula (mass percent) |
| Fluorin modified crylic acid resin | 70 |
| Hydrophobic SiO2 | 5 |
| Microcrystal whisker | 10 |
| Talcum powder | 11 |
| Titanium dioxide | 2 |
| BYK fluorine auxiliary agent | 0.3 |
| BYK defoamer | 0.5 |
| BYK dispersion agent | 0.5 |
| BYK flow agent | 0.7 |
| Amount to | 100 |
By the made coating of above-mentioned formula, its color is white, and its film flexibility reaches 1mm, draws circle sticking power and can arrive 2 grades, and the fresh water contact angle of coatingsurface can reach 130 °, and the sticking power of ice is only 9.5 × 10
3n, more than the sticking power of itself and base material can reach 4MPa, salt spray resistance 1000h paint film is non-foaming, do not come off, non-corroding, but because painting color be white, and xanthochromia and contaminated etc. easily occurs.
Embodiment bis-: first, second component proportion is 12.5:1, wherein second component is isocyanic ester " HDI " tripolymer N3390;
The table composed as follows of first component:
| Starting material | Formula (mass percent) |
| Fluorin modified crylic acid resin | 75 |
| Hydrophobic SiO2 | 3 |
| Microcrystal whisker | 8 |
| Talcum powder | 9 |
| Titanium dioxide | 3 |
| Acetylene black | 0.18 |
| Tai Celadon indigo plant | 0.02 |
| Iron oxide yellow | 0.30 |
| BYK fluorine auxiliary agent | 0.1 |
| BYK defoamer | 0.4 |
| BYK dispersion agent | 0.4 |
| BYK flow agent | 0.6 |
| Amount to | 100 |
The coating that formula obtains is thus for light grey, performance is similar to embodiment mono-coating property, but its weather resistance is better, and salt spray resistance, wet-heat resisting 1500h paint film be non-foaming, do not come off, non-corroding, but its hydrophobic performance slightly declines, the fresh water contact angle of coatingsurface is 124 °.
Embodiment tri-: first, second component proportion is 15:1, wherein second component is isocyanic ester " HDI " tripolymer N3390;
The table composed as follows of first component:
| Starting material | Formula (mass percent) |
| Fluorin modified crylic acid resin | 80 |
| Hydrophobic SiO2 | 2 |
| Microcrystal whisker | 5 |
| Talcum powder | 6 |
| Titanium dioxide | 2 |
| Acetylene black | 0.2 |
| BYK fluorine auxiliary agent | 0.3 |
| BYK defoamer | 0.5 |
| BYK dispersion agent | 0.3 |
| BYK flow agent | 0.7 |
| Amount to | 100 |
In this formula, the PVC of coating is less than the first two embodiment, and more than its sticking power can reach 6MPa, the fresh water contact angle of coatingsurface is 120 °, but its cost has improved 20% left and right.
The present invention is in order to make coating have good hydrophobicity and the easy low surface energy characteristic such as deicing, and with the adhesion property of base material excellence and excellent weather resistance, the present invention is achieved through the following technical solutions:
(1) select and there is excellent low surface energy and the fluorin modified crylic acid resin of weathering resistance:
Organic fluorine coating is due to fine and close molecular structure, there is skin friction coefficient low, coating surface lured voltage high (resistivity is high), surface can be low, is difficult for causing static etc., dust, moisture are difficult to be attached to film coated surface, thereby have remarkable antifouling property.Meanwhile, the optical transmittance of organic fluorine is high, and chemical stability is good, can resist the redoxomorphism of photocatalyst, is unlikely to short-term efflorescence, comes off.
(2) select the micron with acicular structure, the nano level color stuffing that can form " lotus leaf effect ":
Utilize Marangoni effect (Marangonic effect), in solidification process, by selecting nano-inorganic substance particle, micron order color stuffing and needle-like microcrystal to form cross structure, cause being separated and the gathering of nanoparticle in curing of coating process, the dual structure that cured paint film surface formation micrometer structure and nanostructure are combined, this structure can make to hold back a large amount of air filled cavitys in the contact surface of water droplet and solid, form a kind of compound interface, thereby reach surface super hydrophobic performance and easily deicing.
It is base-material that the present invention has best low surface energy fluorin modified crylic acid resin by employing, taking nano level water drain silica as filler, utilize the end acicular structure of polyacrylonitrile nanofiber, give intensity that coating is certain and the microcosmic surface of certain roughness, make coating under wet environment, reduce the water contact area surperficial with it, in making water droplet be difficult to adhere in coating, the adhesion strength of ice in coating also reduces greatly, thereby realizes high hydrophobicity and deicing.The low surface energy anti-icing paint that the present invention is synthetic, coatingsurface has good hydrophobic nature and easily deicing, can reach 130 ° with fresh water contact angle at normal temperatures, ice is only 9.5 × 103N at its surperficial sticking power, and existing low surface energy fluorine carbon coating, ice is 2.1 × 104N at its surperficial sticking power, by contrast, the easy deicing performance of coating that this patent is applied for obtains fine performance, and more than the adhesion strength of coating and base material can arrive 4MPa.
Part not in the detailed description of the invention is prior art.
The embodiment selecting in this article for open object of the present invention, currently thinks suitablely, still, will be appreciated that, the present invention is intended to comprise that all belong to all changes and the improvement of the embodiment in this design and invention scope.
Claims (10)
1. a coating for the easy deicing of low surface energy, is characterized in that: described coating comprises first component and second component, and described first component comprises following composition by mass percentage:
Fluorin modified crylic acid resin 70～80%;
Hydrophobic SiO
22～4%;
Microcrystal 6～10%;
Color stuffing 8～15%;
Auxiliary agent 2～3%;
Described second component is isocyanate trimerization body;
The ratio of described first component and second component is 10～15:1.
2. the coating of the easy deicing of low surface energy according to claim 1, is characterized in that: the solid content of described fluorin modified crylic acid resin base-material is 40～80%.
3. the coating of the easy deicing of low surface energy according to claim 1, is characterized in that: described hydrophobic SiO
2the SiO being replaced by silane group for surface hydroxyl 50～80%
2.
4. the coating of the easy deicing of low surface energy according to claim 1, is characterized in that: described microcrystal is the whisker with acicular structure.
5. the coating of the easy deicing of low surface energy according to claim 1, it is characterized in that: the pigment in described color stuffing is any one in carbon black or phthalocyanine blue or iron oxide yellow or titanium dioxide, and filler is one or both in talcum powder or sericite in powder or ground barium sulfate.
6. the coating of the easy deicing of low surface energy according to claim 1, is characterized in that: described auxiliary agent is any one in BYK series defoamer or flow agent or dispersion agent or fluorine auxiliary agent.
7. the coating of the easy deicing of low surface energy according to claim 1, is characterized in that: described isocyanate trimerization body is isocyanic ester " HDI " tripolymer N3390.
8. the preparation method who utilizes the coating of the easy deicing of a kind of low surface energy of the coating of the easy deicing of a kind of low surface energy described in the arbitrary claim of claim 1～7, is characterized in that: described preparation method specifically comprises the steps:
One, preparation first component:
By the fluorin modified crylic acid resin, the hydrophobic SiO that accurately weigh
2, microcrystal and auxiliary agent put into charging basket, with high speed dispersor stirring at low speed 10～15min, after being uniformly dispersed, add color stuffing according to many principles after heavy after first light, first few again, then high-speed stirring 30～60min, after being uniformly dispersed, grind again 2～3h to coating fineness below 40 μ m, then detect viscosity, detect after qualified and obtain first component through filtration, discharging, packaging;
Two, prepare coating:
Connect step, the first component that the first step is obtained and second component are mixed by the proportioning of 10～15:1, after employing stirrer stirs, can obtain required coating.
9. the preparation method of the coating of the easy deicing of low surface energy according to claim 8, is characterized in that: the speed of described high-speed stirring is 1500～2000r/min.
10. the preparation method of the coating of the easy deicing of low surface energy according to claim 8, is characterized in that: the speed of described stirring at low speed is 400～800 r/min.
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Cited By (3)
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| CN105621961A (en) * | 2015-12-26 | 2016-06-01 | 铃鹿复合建材（上海）有限公司 | Lotus-leaf-type texture coating |
| CN108610780A (en) * | 2016-12-02 | 2018-10-02 | 洛阳尖端技术研究院 | A kind of fluorocarbon resin coating and preparation method thereof |
| CN110922893A (en) * | 2019-11-21 | 2020-03-27 | 国网江西省电力有限公司电力科学研究院 | Hydrophobic self-cleaning anti-icing composite coating and preparation method thereof |
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Cited By (3)
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| CN105621961A (en) * | 2015-12-26 | 2016-06-01 | 铃鹿复合建材（上海）有限公司 | Lotus-leaf-type texture coating |
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| CN110922893A (en) * | 2019-11-21 | 2020-03-27 | 国网江西省电力有限公司电力科学研究院 | Hydrophobic self-cleaning anti-icing composite coating and preparation method thereof |
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