CN100374520C - Anti-fouling ship paint with low biological surface energy - Google Patents
Anti-fouling ship paint with low biological surface energy Download PDFInfo
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- CN100374520C CN100374520C CNB2006100384473A CN200610038447A CN100374520C CN 100374520 C CN100374520 C CN 100374520C CN B2006100384473 A CNB2006100384473 A CN B2006100384473A CN 200610038447 A CN200610038447 A CN 200610038447A CN 100374520 C CN100374520 C CN 100374520C
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- surface energy
- paint
- antifouling
- chitin
- biological surface
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Abstract
The present invention discloses antifouling ship paint with low biologic surface energy, which is composed of low surface energy resin, biologic extract (nonivamide and chitin) microcapsules, nanometer titania, microporous silica and a solvent. The present invention uses the nonivamide and the chitin as an antifoulant slow released by the microcapsules, and combines with the advantages of nanometer modified paint with low surface energy so as to prevent fouling from multiple aspects. The antifouling ship paint is mainly used for antifouling treatment on sea ships, and is also used for second anti-corrosive treatment on bridges, anti-corrosive antifouling treatment on marine engineering members, etc., because the paint has the advantages of self-cleaning, corrosion resistance, high temperature resistance, weather resistance, etc.
Description
Technical field:
The present invention relates to antifouling paint, particularly the marine ship antifouling paint.
Background technology
Nearly more than 2000 kinds of settled organismes in the marine site all over the world, larva of these settled organismes and spore be floating in the ocean, move about, and grows when them and to a certain degree just adhere to alow, settle down and further breeding.These biological attachment can increase the hull bottom surfaceness, make speed of a ship or plane decline, the fuel consumption of boats and ships increase (can reach 30%), also can increase the seawater pipeline transporting resistance, simultaneously, these biologies also can secrete organic acid, and corrosion failure aggravation, the work-ing life of hull bottom steel plate and underwater facility are significantly shortened.Be head it off, various anti-fouling ship paints arise at the historic moment.Once used compounds such as copper, arsenic, cadmium, lead, mercury and tin.Though this can reduce or eliminate halobiontic stained, the release of objectionable impurities has also caused serious harm for ecotope and human health.The early stage compounds such as arsenic, mercury that use of countries such as American and Britain are prepared antifouling paint as stain control agent, because its toxicity is eliminated greatly and already very much.After the seventies in 20th century, because the forbidding of stain control agents such as mercury, arsenic, and find that organotin can reach wide spectrum under lower concentration, antifouling purpose, so organo-tin compound efficiently becomes representational stain control agent.The eighties, find that organotin can accumulate, and causes heritable variation, but also might enter food chain in fish, shellfish body.Afterwards, many in the world countries have carried out considerable research to the toxicity problem of organotin.To the end of the eighties, various countries make laws one after another, forbid or limit the use of the organotin antifouling paint." control boats and ships system's international convention of harmful antifouling end " regulation " rose and forbids that production and use contain poisonous antifouling varnishs such as organotin on January 1st, 2003; Forbade thoroughly that boats and ships use the antifoulant that contains organotin on January 1st, 2008 ".
Bio-extract is the active substance that extracts from natural biological, has the product performance of " only catch up with and do not kill ", can prevent that marine organisms from adhering to boats and ships, the boats and ships of Marine Pollution not again, is a kind of no mutual antifouling paint, and the marine eco-environment is not had destruction.Low surface energy anti-fouling paint is to utilize coating surface to have the physicals of low surface energy, make marine organisms be difficult to adhere to or adhere to not firmly, when ship's navigation, utilize the shear action of water or special cleaning equipment to be easy to remove a kind of antifouling paint of settled organism.
Summary of the invention:
It is long to the purpose of this invention is to provide a kind of antifouling phase, avirulent anti-fouling ship paint with low biological surface energy.
Technical solution of the present invention is:
A kind of anti-fouling ship paint with low biological surface energy is characterized in that: be made up of following composition by weight:
Resin with low surface energy 19～26%
Bio-extract (capsaicine, chitin) microcapsule 0.1～0.2%
Nano titanium oxide 1～2%
Microporous type silica 1 5～20%
Surplus is a solvent.
Resin with low surface energy is the fluoro-silicone resin.Bio-extract (capsaicine, chitin) microcapsule are slow-release microcapsule, mean particle size 0.7～1 μ m.Nano titanium oxide mean particle size 50～70nm significantly improves the physicals of coating, 1 grade of sticking power, shock strength 500N.cm, hardness 3H, 1 grade of salt spray resistance.Microporous type silica average particle size 0.8～1 μ m, pore volume 1.6～1.8ml/g cooperates slow-release microcapsule to play the release regulating effect.Solvent is ethanol or dimethylbenzene or other suitable solvents.
The preparation method of said bio-extract (capsaicine, chitin) microcapsule is as follows:
Dispersed dye, system modifier MS and an amount of distilled water with high shearing mixing emulsor high speed homogenizing 2～5min, are regulated the pH value to slightly acidic, then this mixture is poured into there-necked flask, put into constant temperature water bath, stir with the powerful motor agitator.Drip melmac under the room temperature in bottle, be warming up to 60 ℃ again, behind insulation 1～1.5h, the individual layer wall building is carried out in the cooling cooling; And then in bottle, drip melmac, and being warming up to 75 ℃ again, behind insulation 1.5～2h, double-deck wall building is carried out in cooling, pours out reactant, uses this thing of distilled water wash 2～3 times, leaches micro-capsule dyes, and it is standby to put into moisture eliminator after the oven dry.Capsaicine that the present invention selects for use and chitin as stain control agent microcapsule slowly-releasingization after, its active substance can slowly discharge, and drives marine attaching organism, is 0.1～0.2% together with the total consumption of microcapsule, effective rate of utilization improves greatly.
Show through the sea water simulation test: capsaicine and chitin release rate are stabilized in 70～80 μ gm
-2d
-1, effective antifouling life reached more than 5 years.
The present invention has following effect compared with prior art:
1, the bio-extract antifouling paint has the product performance of " only catch up with and do not kill ", can prevent that marine organisms from adhering to boats and ships, the boats and ships of Marine Pollution not again, is a kind of nontoxic antifouling paint, and the marine eco-environment is not had destruction;
2, the biologically active substance activity is given full play to biological stain control agent microcapsule slowly-releasingization, solved active lasting problem, reduce biological extraction row alive thing content in the antifouling paint significantly;
3, novel nano comprehensive silicon-fluorine surface energy anti-fouling paint is in conjunction with the bio-extract stain control agent, and is antifouling by number of ways.
Embodiment
Embodiment 1:
(1) trimethyl silyl end capped poly-(methyl hydrogen siloxane) and the reaction of nine fluorine hexenes are made resin with low surface energy, add modified nano-titanium dioxide then therein, be prepared into nano combined fluoro-silicone resin, surface energy 1.68 * 10
-4N/m, marine attaching organism is difficult to adhere to.
(2) in reactor, at first add solvent (ethanol or dimethylbenzene, toluene or other solvents) and nano combined fluoro-silicone resin by prescription dosage, after fully stirring, under agitation condition, add bio-extract (capsaicine successively by prescription dosage, chitin) microcapsule, microporous type silicon-dioxide make anti-fouling ship paint with low biological surface energy behind the stirring 30min.
The consumption of above-mentioned each component (weight) is:
Resin with low surface energy 19%
Bio-extract (capsaicine, chitin) microcapsule 0.1%
Nano titanium oxide 2%
Microporous type silica 1 8%
Surplus is a solvent.
This coating evenly is coated with (spray) on steel disc, behind the room temperature airing, is hung in 2 liters of sea water solutions, measure the rate of release and the surface energy variation situation of bio-extract.The result is as follows:
| Time/moon | 1 | 2 | 3 | 4 | 5 | 6 | 12 |
| The rate of release ugm of extract -2d -1 | 71 | 71.5 | 71.3 | 71.2 | 71.4 | 71.3 | 71.6 |
| Surface energy/N/m * 10 4 | 1.68 | 1.68 | 1.68 | 1.68 | 1.68 | 1.68 | 1.68 |
Embodiment 2:
The consumption of each component (weight) is:
Resin with low surface energy 22%
Bio-extract (capsaicine, chitin) microcapsule 0.15%
Nano titanium oxide 1%
Microporous type silicon-dioxide 20%
Surplus is a solvent.All the other are with embodiment 1.
Embodiment 3:
The consumption of each component (weight) is:
Resin with low surface energy 26%
Bio-extract (capsaicine, chitin) microcapsule 0.2%
Nano titanium oxide 1.5%
Microporous type silica 1 5%
Surplus is a solvent.All the other are with embodiment 1.
Claims (3)
1. anti-fouling ship paint with low biological surface energy is characterized in that: be made up of following composition by weight:
Fluoro-silicone resin 19～26%
Bio-extract (capsaicine, chitin) slow-release microcapsule 0.1～0.2%
Nano titanium oxide 1～2%
Microporous type silica 1 5～20%
Surplus is a solvent;
Wherein microporous type silicon-dioxide is meant that pore volume is the silicon-dioxide of 1.6～1.8ml/g.
2. anti-fouling ship paint with low biological surface energy according to claim 1 is characterized in that: nano titanium oxide mean particle size 50～70nm.
3. anti-fouling ship paint with low biological surface energy according to claim 1 is characterized in that: solvent is ethanol or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100384473A CN100374520C (en) | 2006-02-23 | 2006-02-23 | Anti-fouling ship paint with low biological surface energy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100384473A CN100374520C (en) | 2006-02-23 | 2006-02-23 | Anti-fouling ship paint with low biological surface energy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1810903A CN1810903A (en) | 2006-08-02 |
| CN100374520C true CN100374520C (en) | 2008-03-12 |
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| CNB2006100384473A Expired - Fee Related CN100374520C (en) | 2006-02-23 | 2006-02-23 | Anti-fouling ship paint with low biological surface energy |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012109785A1 (en) * | 2011-02-16 | 2012-08-23 | 国家海洋局第一海洋研究所 | Halobios antifouling paint, preparation method and use thereof |
| CN102399487B (en) * | 2011-09-01 | 2013-07-17 | 中国船舶重工集团公司第七二五研究所 | Dimension-adjustable porous micro-structured surface antifouling material |
| CN103694754B (en) * | 2013-12-12 | 2016-01-13 | 青岛海洋新材料科技有限公司 | A kind of Bionic Marine Antifouling Coatings |
| WO2016036550A1 (en) * | 2014-09-05 | 2016-03-10 | Ekomarine Paint Inc. | A method for treating surfaces on marine objects with anti-fouling paint |
| CN105038449A (en) * | 2015-06-30 | 2015-11-11 | 芜湖县双宝建材有限公司 | Wear-resistant high-adhesive force environmental-friendly corrosion-resistant antifouling paint |
| CN105331287B (en) * | 2015-11-17 | 2018-05-11 | 国网河南省电力公司周口供电公司 | A kind of mountain area super-high voltage road surfaces anti-icing nano coating and preparation method thereof |
| CN105965122B (en) * | 2016-06-25 | 2018-12-28 | 天津泊荣石油科技发展有限公司 | A kind of ocean engineering steel surface anti-fouling corrosion resistant alloy and pricker coating method |
| CN106280820A (en) * | 2016-07-27 | 2017-01-04 | 上海巨峰化工有限公司 | A kind of fluorine silicon acrylate paint |
| CN106634131A (en) * | 2016-11-10 | 2017-05-10 | 仇颖超 | Preparation method of environment-friendly marine antifouling coating |
| CN106868441A (en) * | 2017-01-17 | 2017-06-20 | 中国科学院宁波材料技术与工程研究所 | A kind of polymer composite coating and its preparation method and application |
| CN107163814A (en) * | 2017-06-06 | 2017-09-15 | 无锡华东锌盾科技有限公司 | Long-acting and anti-fouling coating and preparation method thereof |
| KR101917149B1 (en) * | 2018-05-17 | 2018-11-09 | 주식회사 대수하이테크 | Anti-fouling coating composition having excellent weatherability |
| CN109985586A (en) * | 2019-03-20 | 2019-07-09 | 华南理工大学 | A kind of anti-biological microcapsules and the preparation method and application thereof |
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|---|---|---|---|---|
| US5397385A (en) * | 1994-03-28 | 1995-03-14 | Watts; James L. | Anti-fouling coating composition containing capsaicin |
| CN1296044A (en) * | 1999-11-12 | 2001-05-23 | 陈光宇 | Low surface energy repelling type dirt-proof paint and use method thereof |
| JP2001207125A (en) * | 2000-01-25 | 2001-07-31 | Masayoshi Tsuchiya | Coating for preventing adhesion of shellfishes |
| CN1477166A (en) * | 2003-07-08 | 2004-02-25 | 贵州慧博科技开发有限公司 | Capsaicin self-polishing antifouling paint and its preparation method |
-
2006
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5397385A (en) * | 1994-03-28 | 1995-03-14 | Watts; James L. | Anti-fouling coating composition containing capsaicin |
| CN1296044A (en) * | 1999-11-12 | 2001-05-23 | 陈光宇 | Low surface energy repelling type dirt-proof paint and use method thereof |
| JP2001207125A (en) * | 2000-01-25 | 2001-07-31 | Masayoshi Tsuchiya | Coating for preventing adhesion of shellfishes |
| CN1477166A (en) * | 2003-07-08 | 2004-02-25 | 贵州慧博科技开发有限公司 | Capsaicin self-polishing antifouling paint and its preparation method |
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| 辣素防污涂料在海洋网箱网衣材料中的应用. 史航，王鲁民.大连水产学院学报，第20卷第4期. 2005 * |
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| CN1810903A (en) | 2006-08-02 |
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Owner name: JIANGSU GEMEIGAO TECHNOLOGY DEVELOPMENT CO., LTD. Free format text: FORMER NAME: NANTONG KEXING CHEMICAL CO., LTD. |
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Address after: 226009, Zhenxing Road, Nantong economic and Technological Development Zone, Jiangsu 19, China Patentee after: Jiangsu Gemei High-Tech Development Co., Ltd. Address before: 226009, Zhenxing Road, Nantong economic and Technological Development Zone, Jiangsu 19, China Patentee before: Nantong Kexing Chemical Industry Co., Ltd. |
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Denomination of invention: Anti-fouling ship paint with low biological surface energy Effective date of registration: 20160805 Granted publication date: 20080312 Pledgee: Suitable financial information service (Shanghai) Co., Ltd. Pledgor: Jiangsu Gemei High-Tech Development Co., Ltd. Registration number: 2016980000116 |
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