CN101260262B - Antifouling material capable of forming concave-convex micro-structure surface and preparation method thereof - Google Patents
Antifouling material capable of forming concave-convex micro-structure surface and preparation method thereof Download PDFInfo
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- CN101260262B CN101260262B CN2008100933732A CN200810093373A CN101260262B CN 101260262 B CN101260262 B CN 101260262B CN 2008100933732 A CN2008100933732 A CN 2008100933732A CN 200810093373 A CN200810093373 A CN 200810093373A CN 101260262 B CN101260262 B CN 101260262B
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Abstract
本发明涉及一种防污材料及其制备方法，特别是一种针对海洋环境条件下，防除船舶及海洋结构物表面附着海生物的通过直接成膜可形成凹凸微结构表面的防污材料及其制备方法，属于海洋生物污损防护领域，将可水解释放硅油的丙烯酸树脂、含防污活性功能基团的改性硅树脂、甲基硅树脂按1∶1∶2的体积比在容器中摇动并混合后静置2-3小时，再加入总体积0.3～0.6％的三乙烯四胺作为固化剂在同一容器中混合并摇匀制得防污材料溶液，使用时涂膜形成具有规律性的凹凸微结构表面，与现有技术及产品相比具有较好的防止海洋生物附着和污损的效果，且无环境污染问题。The invention relates to an antifouling material and a preparation method thereof, in particular to an antifouling material capable of forming a concave-convex microstructure surface through direct film formation for preventing marine organisms from adhering to the surface of ships and marine structures under marine environmental conditions and its The preparation method belongs to the field of marine biofouling protection, and the acrylic resin that can release silicone oil by hydrolysis, the modified silicone resin containing antifouling active functional groups, and methyl silicone resin are shaken in a container according to the volume ratio of 1:1:2. After mixing, let it stand for 2-3 hours, then add 0.3-0.6% triethylenetetramine as a curing agent in the same container, mix and shake well to obtain an antifouling material solution, and the coating film will form a regular pattern when used. Compared with the prior art and products, the concave-convex microstructure surface has a better effect of preventing marine organisms from attaching and fouling, and has no environmental pollution problem.
Description
Technical field:
The present invention relates to a kind of anti-fouling material and preparation method thereof, particularly a kind of under the ocean environment condition, prevent and kill off passing through direct film forming and can forming anti-fouling material of concave-convex micro-structure surface and preparation method thereof of boats and ships and marine structure surface attachment marine life, belong to marine biofouling protection field.
Background technology:
At present, exist a large amount of marine organisms in the seawater, these marine organisms can adhere to the boats and ships and the generation of works surface that are in for a long time in the briny environment, and this adhewsive action can increase the running resistance of boats and ships, have a strong impact on the route speed of boats and ships, increase fuel oil consumption, also can destroy the corrosion protection coating on boats and ships and works surface simultaneously, thereby cause the corrosion breakage on hull and works surface, have a strong impact on its security.Therefore seeking suitable way prevents that marine organisms from having very important significance to stained the adhering to of boats and ships and marine structure.
The existing main path that is used for preventing marine biofouling is exactly the external coating antifouling paint at boats and ships housing and marine structure, and this class coating mainly is to contain organotin, Red copper oxide or DDT, to carry out antifouling by contained stain control agent to the strong toxic action of organism.But this class coating adheres to the halobiontic while in poisoning, also can do great damage to the marine eco-environment, and use progressively is being under an embargo.
Owing to take place halobiontic adhering at material surface, if therefore can effectively change the wetting property of material surface, improve hydrophobic ability, can reduce or reduce the possibility that marine organisms adhere to effectively, and because this mode can not produce damaging influence to ocean environment, so can provide the important technology approach for preparing nontoxic anti-fouling material.Studies show that, influence the infiltrating factor of solid surface and mainly contain two: the one, surface free energy; The 2nd, surface microstructure.When Solid Surface Free Energy reduced, hydrophobic performance will be enhanced, but the minimum surface that can access material at present can only can reach 6.7mJ/m
2, promptly by-CF
3Group is the compact arranged surface of sexangle, but the contact angle of its smooth surface and water also has only 119 °.Therefore,, make up surface micro-structure, change surfaceness and just become extremely important in order to obtain better hydrophobic effect.
Carrying out comparatively deep research aspect the low surface energy anti-fouling material both at home and abroad, but the practical application effect of such material is unsatisfactory.Subject matter is exactly still to have the part marine organisms to adhere in its surface generation, and these settled organismes must can obtain removing by external force.The reason that causes present low-surface-energy material the problems referred to above is exactly only to be that to rely on the low surface energy feature of material itself to carry out antifouling when being used to be prepared anti-fouling material, and hydrophobic effect is limited.For addressing this problem, domestic some low surface energy anti-fouling materials newly developed all combine with stain control agent at present, further improve anti-fouling effect.As publication number is CN1810903, title is the patent of anti-fouling ship paint with low biological surface energy, a kind of anti-fouling ship paint with low biological surface energy by resin with low surface energy, bio-extract (capsaicine, chitin) microcapsule, nano titanium oxide, microporous type silicon-dioxide and solvent composition is disclosed; Publication number is CN1296044A, the name be called low surface energy, repelling type dirt-proof paint and using method thereof patent disclosure a kind of environmental protection antifouling paint of forming by binding material, silane coupling agent, fluorochemicals, the natural stain control agent of pungent type, mineral filler and solvent.These prior arts are utilizing low-surface-energy material further to make up micro-structure surface, improve hydrophobicity, improve aspect such as anti-fouling effect and also relatively lack.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that exists in the prior art, design a kind of anti-fouling material and preparation method thereof at preventing and kill off boats and ships and the adhering to marine life of marine structure surface in the ocean environment, this material is discharged the acrylic resin of silicone oil by hydrolyzable, be prepared from after containing the modified silicone resin of antifouling activity functional group by volume ratio being mixed with methyl silicon resin, the back formation of filming has the surface of regular concave-convex micro-structure, thereby the hydrophobicity of this material is significantly improved, can prevent halobiontic stained better, this material does not use stain control agent, and environment is not had damaging influence.
To achieve these goals, anti-fouling material that the present invention relates to and preparation process thereof be with hydrolyzable discharge the acrylic resin of silicone oil, the modified silicone resin that contains the antifouling activity functional group, methyl silicon resin shake in container by 1: 1: 2 volume ratio and mix after left standstill 2-3 hour, the triethylene tetramine that adds cumulative volume 0.3～0.6% again mixes and shakes up in same container as solidifying agent and makes anti-fouling material solution, films to form to have regular concave-convex micro-structure surface.
The acrylic resin that the used hydrolyzable of the present invention discharges silicone oil is a hydroxyl silicon oil modified acrylic resin, and its structural formula is:
X1, X2 are H or CH in the formula
3R is the alkyl chain of C1-C7; M is the natural number of 2-12, and n is the natural number of 1-3; A is O element or NH
2Group; R1, R2 are the alkyl chain of C1-C7.
The modified silicone resin that contains the antifouling activity functional group that the present invention is used is the silane coupler modified acrylic resin of suspended side chain paeonol structure, and its structural formula is:
X is H or CH in the formula
3, B is the part of unsaturated vinyl monomer remainder.
Among the present invention related material be by hydrolyzable discharge silicone oil acrylic resin, contain the antifouling activity functional group modified silicone resin with make after methyl silicon resin mixes by a certain percentage, this material is after adding the triethylene tetramine solidifying agent, film and to form surface with regular concave-convex micro-structure, the diatom larva of filming in the laboratory that forms adheres to experiment and real extra large link plate biological attachment experiment shows, have and prevent that preferably marine life from adhering to and stained effect, and the non-environmental-pollution problem.
Embodiment:
The present invention will be further described below by embodiment.
Embodiment 1:
Measure methyl silicon resin 40ml earlier and put into reaction vessel, the acrylic resin 20ml of measuring hydrolyzable release silicone oil more respectively adds in the container with the modified silicone resin 20ml that contains the antifouling activity functional group, shake and mix, left standstill 2 hours, measure solidifying agent triethylene tetramine 0.24 μ l then and add in the same container, remix also shakes up and promptly gets anti-fouling material solution.
Embodiment 2:
Measure methyl silicon resin 80ml earlier and put into reaction vessel, the acrylic resin 40ml of measuring hydrolyzable release silicone oil more respectively adds in the container with the modified silicone resin 40ml that contains the antifouling activity functional group, shake it is mixed, left standstill 2.5 hours, measure solidifying agent triethylene tetramine 0.80 μ l adding then and make in the same container of material, mix and shake up promptly getting anti-fouling material solution.
Embodiment 3:
Measure methyl silicon resin 120ml earlier and put into reaction vessel, the acrylic resin 60ml of measuring hydrolyzable release silicone oil more respectively adds in the container with the modified silicone resin 60ml that contains the antifouling activity functional group, shake it is mixed, left standstill 3 hours, measuring solidifying agent triethylene tetramine 1.4 μ l adding then makes in the same container of material, mix, shake up and promptly get anti-fouling material solution.
Embodiment 4:
Get one of clean 40mm * 10mm * 5mm sheet glass, the anti-fouling material solution that adds solidifying agent and mixing and make is filmed on sheet glass, after the curing, under electron microscope, observe, i.e. the occurrence law concave-convex micro-structure surface; Adopt three anti-fouling material solution experiments among the embodiment repeatedly, its result is all good.
Get the sheet glass of filming and blank glass plate and carry out indoor diatom and adhere to simultaneous test, after the week, the coated glass plate does not have the diatom attachment phenomenon and occurs, and the blank glass plate of the contrast then area more than 85% diatom occurs and adheres to.
Claims (1)
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| CN2008100933732A CN101260262B (en) | 2008-04-15 | 2008-04-15 | Antifouling material capable of forming concave-convex micro-structure surface and preparation method thereof |
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| CN2008100933732A CN101260262B (en) | 2008-04-15 | 2008-04-15 | Antifouling material capable of forming concave-convex micro-structure surface and preparation method thereof |
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| CN101260262B true CN101260262B (en) | 2011-02-02 |
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| CN102417792B (en) * | 2011-11-23 | 2013-06-12 | 中国船舶重工集团公司第七二五研究所 | Preparation method of antifouling material having crossed regular microstructure on surface |
| JP6438564B2 (en) | 2014-04-03 | 2018-12-12 | ピーピージー コーティングス ヨーロッパ ベーヴェー | Erosive antifouling coating composition |
| KR101517877B1 (en) * | 2014-09-03 | 2015-05-07 | 주식회사 신도디앤텍 | Coating sheet for preventing adhesion of advertising material |
| CN106700905A (en) * | 2015-11-13 | 2017-05-24 | 肇庆华欣特化工涂料有限公司 | Nano car coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1742064A (en) * | 2003-01-27 | 2006-03-01 | 大金工业株式会社 | coating composition |
| CN101011061A (en) * | 2006-12-05 | 2007-08-08 | 中国船舶重工集团公司第七二五研究所 | Biological antistain agent with low surface energy characteristic and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1742064A (en) * | 2003-01-27 | 2006-03-01 | 大金工业株式会社 | coating composition |
| CN101011061A (en) * | 2006-12-05 | 2007-08-08 | 中国船舶重工集团公司第七二五研究所 | Biological antistain agent with low surface energy characteristic and its preparing process |
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| Title |
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| JP特开2002-265849A 2002.09.18 |
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