CN101550306A - Universal ship bottom antifouling coating - Google Patents
Universal ship bottom antifouling coating Download PDFInfo
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- CN101550306A CN101550306A CNA2008100888629A CN200810088862A CN101550306A CN 101550306 A CN101550306 A CN 101550306A CN A2008100888629 A CNA2008100888629 A CN A2008100888629A CN 200810088862 A CN200810088862 A CN 200810088862A CN 101550306 A CN101550306 A CN 101550306A
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Abstract
The invention discloses universal ship bottom antifouling coating, and relates to universal high-solid self-polishing ship bottom antifouling coating, in particular to novel marine antifouling coating containing an antifouling agent system without cuprous oxide and other internationally non-permissible toxins and reaching the national environment-friendly requirements. The universal ship bottom antifouling coating is characterized by comprising zinc acrylate resin, composite antifouling agents, pigments, fillers, anti-sedimentation agents, solvents, and the like and being of various colors. The coating is applicable to marine engineering or a ship bottom as an antifouling coating, can be used at aluminum substrate surfaces, steel substrate surfaces and waterline positions, can effectively prevent the ship bottom from fouling by marine organisms within 1-2 years, is environment-friendly and constructed conveniently, can keep the speed of a ship uninfluenced, and saves fuel; and the coating further has good overcoatability.
Description
Technical field
The present invention relates to a kind of antifouling paint, especially refer to a kind of universal high solid antifouling varnish at the bottom of polishing type ship that has, can be used for aluminium matter, steel substrate surface and waterline position, cuprous and other the international poison material forbidden of oxygen-freeization reach national requirements for environmental protection.
Background technology
The sail in a mighty ocean primary difficult problem that run into of boats and ships is exactly marine life adhering to stained hull bottom.Surplus the marine organisms of now tentatively verifying reach 20 ten thousand kinds, part biological is with the fixed object apposition growth, and the underwater hull bottom is the main base of biological attachment, and marine life adheres to ship's navigation and brought very big harm.Up to 20 kilograms, they increase the hull bottom roughness to China Nanhai area marine organisms at growth busy season every square metre of adhesion amount, reduce the speed of a ship or plane, increase fuel oil consumption.According to statistics, the fuel cost flower that half is arranged every year was the deceleration that causes was lost efficacy in compensation owing to antifouling varnish on, and ten thousand tons of ocean-going freighters of a bow if hull bottom adheres to the stained of 10% area, can bring 1,000,000 dollars loss.And, antifouling paint antirust for recoat also will spend a large amount of depressed places that accounts for and take and remuneration.Therefore, develop efficient antifouling paint, be the most important problem of marine finish research field always.
Antifouling varnish is a kind of special coating, it progressively is discharged into low-down speed by the activeconstituents (toxic agent) that will be comprised and suppresses in the seawater and stop marine life adhering to and grow on ocean steel constructions such as boats and ships, thereby the smooth and coating of maintenance hull outside surface is intact, under the prerequisite that guarantees the normal speed of a ship or plane, reduce oil consumption to greatest extent and prolong the work-ing life of coating, reduce unnecessary expenditures for maintenance.
Matrix used material mainly is steel ship and wooden boat before the antifouling varnish, and along with the development of shipbuilding industry, aluminium matter ship engenders, requires can not contain Red copper oxide (Cu in the antifouling varnish
2O), can not cause galvanic corrosion, make hull corrosion occur, therefore, the antifouling varnish system proposed new requirement because of oozing out of cupric ion.In addition, boats and ships waterline position, long-term Exposure to Sunlight and alternation of wetting and drying, Red copper oxide (Cu
2O) easy oxygenolysis and lose anti-fouling effect also is not suitable for adding.International Maritime Organizaton also can limit Red copper oxide (Cu in 2012 after banning use of organotin (TBT) and DDT poison material
2O) use, therefore, the cuprous (Cu of development of new oxygen-freeization
2O) antifouling varnish is urgent and necessary.
At present, each big paint company is to be matrix resin with vinylformic acid copper, zinc acrylate resin or vinylformic acid silica alkane, with Red copper oxide (Cu substantially
2O) be main stain control agent.The zinc acrylate resin that this invention is selected for use, consider the universal of antifouling varnish, especially at aluminium matter hull and waterline position, monomer, initiator, solubility promoter etc. have been carried out meticulous selection, and conditions such as temperature of reaction, reaction times, monomer dropping speed are optimized, filter out the best synthesis technique of acrylic resin at last, synthesized required zinc acrylate resin.Compound organic stain control agent that the present invention adopts, by cuprous thiocyanate (CuSCN), Zinc Pyrithione, Seanine211 (4,5-two chloro-2-n-octyls-3-isothiazole copper), zineb Zineb (the two dithio first propylhomoserin zinc of ethylene) forms, can progressively discharge along with the hydrolysis of resin and ooze out, effectively prevent the apposition growth of all kinds of marine lifes.
Therefore, domestic coating variety does not also have the cuprous (Cu of a kind of oxygen-freeization
2O) and the organotin (TBT) of international forbidding and DDT poison material, have environmental protection characteristic, easy construction, what have characteristics of the present invention universally polishes antifouling varnish at the bottom of the type ship certainly.As ZL97121813.7 described " non-toxic anti-pollution paint for sea " is to be main resin binder with silicate, and organic stain control agent that is added and kind of the present invention and content are all inequality.ZL98119956.9 described " silicate compound anti-fouling paint " also is to be main resin binder with silicate, adds the antifouling composition identical with the present invention.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of environmental protection characteristic that has, the cuprous (Cu of oxygen-freeization
2O) and the organotin (TBT) of international forbidding and DDT poison expect, can be used for antifouling varnish at the bottom of the type ship of polishing certainly at aluminium matter, steel substrate surface and waterline position.
The present invention also provides the preparation method of described antifouling paint.
The object of the present invention is achieved like this:
Universal ship bottom antifouling paint wherein comprises following composition: prescription by weight is:
(1) zinc acrylate resin: 20～40 weight parts
(2) compound organic stain control agent: 20～30 weight parts
(3) face, filler: talcum powder 2～3 weight parts, zinc oxide 8～12 weight parts
(4) mixed solvent is: dimethylbenzene 10～20 weight parts, N-BUTYL ACETATE 5～10 weight parts
(5) dispersion agent is: methoxyl group ester propyl propionate solution 0.2～0.5 weight part
(6) anti-settling agent: organobentonite 2～4 weight parts
Compound organic stain control agent material described in the present invention is: cuprous thiocyanate (CuSCN) 5～10 weight parts, Zinc Pyrithione 5～10 weight parts, Seanine 211 (4,5-two chloro-2-n-octyls-3-isothiazole copper) 2～5 weight parts, zineb Zineb (the two dithio first propylhomoserin zinc of ethylene) 2～5 weight parts.
The preparation method of the universal ship bottom antifouling coating described in the present invention, may further comprise the steps: make zinc acrylate resin all be dissolved in the mixed solvent, fully dissolving, add successively and mix organic stain control agent, dispersion agent, face, filler, anti-settling agent, stir, high speed dispersion, high speed dispersion once more after the grinding; After detecting viscosity, fineness, obtain coating.
The coating process of the universal ship bottom antifouling coating described in the present invention:
General application 3～4 roads, coating thickness need reach 200～300 μ m, the construction of different methods such as available airless spraying, brushing or roller coating.High solid, one build of airless spraying can reach 100 μ m.When film thickness reaches specified requirement, can reach effective anti-fouling effect.
Embodiment
Below the present invention will be described in detail by two specific exampless:
Embodiments of the invention one are " 859 universal ship bottom antifouling coating ", and prescription by weight is:
(1) zinc acrylate resin: 30 weight parts
(2) compound organic stain control agent: 22 weight parts, cuprous thiocyanate (CuSCN) 10 weight parts wherein, Zinc Pyrithione 5 weight parts, Seanine 211 (4,5-two chloro-2-n-octyls-3-isothiazole copper) 3 weight parts, zineb Zineb (the two dithio first propylhomoserin zinc of ethylene) 4 weight parts
(3) pigment: talcum powder 3 weight parts, zinc oxide 10 weight parts, blue 0.2 weight part of phthalein cyanogen
(4) mixed solvent is: dimethylbenzene 15 weight parts, N-BUTYL ACETATE 5 weight parts
(5) dispersion agent is: methoxyl group ester propyl propionate solution 0.2 gram
(6) anti-settling agent: organobentonite 2 grams
The preparation method is as follows:
Earlier zinc acrylate resin all is dissolved in the mixed solvent, fully dissolving adds compound organic stain control agent, dispersion agent, face, filler, anti-settling agent successively, stirs, high speed dispersion high speed dispersion once more after the grinding; After detecting viscosity, fineness, obtain coating.
This coating detects result such as table one according to standard GB/T 6822-1986 " ship bottom anti-fouling paint general technical specifications "
The key technical indexes of table one, " 859 universal ship bottom antifouling coating "
| Test item | Technical indicator | Check data |
| Color and outward appearance | Blue look | Conformance with standard |
| Viscosity (being coated with-4,25 ℃), S | 60-80 | 60 |
| Proportion, g/cm 3 | About 1.72 | 1.72 |
| Fineness, μ m | ≤ 80 | 60 |
| Time of drying, h | Surface drying≤4, do solid work≤24 | Surface drying 4 does solid work 24 |
| Sticking power (drawing the circle method), level | 1-2 | 1 |
| Snappiness, mm | 1 | 1 |
| Shock strength, cm | 〉=40 | 50 |
| Solids content, % | 〉=60 | 62 |
| Theoretical lacquer amount, the Kg/m of using 2. the road | 0.304 | Conformance with standard |
| Standard film thickness, μ m/ road | 〉=80 | 100 |
| Antifouling property | The antifouling phase of 1-2 imitates | Conformance with standard |
| Dynamic antifouling property | 〉=3 cycles | Through 3 periodic tests: 859 universal ship bottom antifouling coating model paint films are intact, do not have bubbles, come off, the surperficial no marine life of model adheres to. |
| Shelf lives, a | 〉=1 | Conformance with standard |
859 universal ship bottom antifouling coatings of the present invention have following performance characteristics:
1, the cuprous (Cu of oxygen-freeization
2O) and the organotin (TBT) of international forbidding and DDT poison expect to have environmental protection characteristic.
2, can be used for aluminium matter hull bottom, the protection phase with 1-2 imitates.
3, well attached with the hull bottom coating, have excellent physical and mechanical properties, even the shipping high speed navigation can not come off yet, highest speed can reach 40 joints.
4, paint film keeps smooth surface, can keep ship's speed unaffected, fuel saving.
5, easy construction, the construction of different methods such as available airless spraying, brushing or roller coating.High solid, one build of airless spraying can reach 100 μ m.
6, have good drying property, the four seasons all can use, and can construct under various weather condition.
Embodiments of the invention two are " 857 vinylformic acid waterline antifouling varnish ", and prescription by weight is:
(1) zinc acrylate resin: 30 weight parts
(2) compound organic stain control agent: 22 weight parts, cuprous thiocyanate (CuSCN) 10 weight parts wherein, Zinc Pyrithione 5 weight parts, Seanine 211 (4,5-two chloro-2-n-octyls-3-isothiazole copper) 4 weight parts, zineb Zineb (the two dithio first propylhomoserin zinc of ethylene) 3 weight parts
(3) pigment: talcum powder 3 weight parts, zinc oxide 10 weight parts, red 0.2 weight part of sun-proof
(4) mixed solvent is: dimethylbenzene 15 weight parts, N-BUTYL ACETATE 8 weight parts
(5) dispersion agent is: methoxyl group ester propyl propionate solution 0.2 gram
(6) anti-settling agent: organobentonite 2 grams
The preparation method is as follows:
Earlier zinc acrylate resin all is dissolved in the mixed solvent, fully dissolving adds compound organic stain control agent, dispersion agent, face, filler, anti-settling agent successively, stirs, high speed dispersion high speed dispersion once more after the grinding; After detecting viscosity, fineness, obtain coating.
This coating detects result such as table two according to standard GB/T 6822-1986 " ship bottom anti-fouling paint general technical specifications "
The key technical indexes of table two, " 857 vinylformic acid waterline antifouling varnish "
| Test item | Technical indicator | Check data |
| Color and outward appearance | Of all kinds | Conformance with standard |
| Viscosity (being coated with-4,25 ℃), S | 60-80 | 60 |
| Proportion, g/cm 3 | About 1.68 | 1.68 |
| Fineness, μ m | ≤80 | 60 |
| Time of drying, h | Surface drying≤4, do solid work≤24 | Surface drying 4 does solid work 24 |
| Sticking power (drawing the circle method), level | 1-2 | 1 |
| Snappiness, mm | 1 | 1 |
| Shock strength, cm | ≥40 | 50 |
| Solids content, % | 〉=60 | 65 |
| Theoretical lacquer amount, the Kg/m of using 2. the road | 0.304 | Conformance with standard |
| Standard film thickness, μ m/ road | 〉=80 | 100 |
| Antifouling property | The antifouling phase of 1-2 imitates | Conformance with standard |
| Dynamic antifouling property | 〉=3 cycles | Through 3 periodic tests: 857 vinylformic acid waterline antifouling varnish model paint films are intact, do not have bubbles, come off, the surperficial no marine life of model adheres to. |
| Shelf lives, a | 〉=1 | Conformance with standard |
857 acrylic acid waterline anti-fouling paints of the present invention have following performance characteristics:
1, the cuprous (Cu of oxygen-freeization2O) and the organotin (TBT) of international forbidding and DDT poison expect to have environmental protection characteristic.
2, can be used for the waterline position and prevent the stained of marine growth, prevent solar exposure, have the protection phase effect of 1-2.
3, well attached with the hull bottom coating, have good physical and mechanical properties.
4, paint film keeps smooth surface, can keep ship speed unaffected, fuel saving.
5, easy construction, the construction of the distinct methods such as available airless spraying, brushing or roller coating. High solid, one build of airless spraying can reach 100 μ m.
6, have good drying property, the four seasons all can use, and can construct under various weather conditions.
Claims (6)
1. universal ship bottom antifouling coating, especially refer to contain compound stain control agent system, cuprous and other the international poison material forbidden of oxygen-freeization, reach the novel sea antifouling paint of national requirements for environmental protection, it is characterized in that: form by zinc acrylate resin, compound stain control agent, face, filler, anti-settling agent, solvent etc., of all kinds, this coating is applicable to that oceanographic engineering or hull bottom position use as antifouling varnish, can be used for aluminium matter, steel substrate surface and waterline position, can in 1-2, effectively prevent marine life stained to hull bottom.
2. universal ship bottom antifouling coating according to claim 1 is characterized in that, wherein:
Comprise following composition: prescription by weight is:
(1) zinc acrylate resin: 20～40 weight parts
(2) compound organic stain control agent: 20～30 weight parts
(3) pigment: talcum powder 2～3 weight parts, zinc oxide 8～12 weight parts
(4) mixed solvent is: dimethylbenzene 10～20 weight parts, N-BUTYL ACETATE 5～10 weight parts
(5) dispersion agent is: methoxyl group ester propyl propionate solution 0.2～0.5 weight part
(6) anti-settling agent: organobentonite 2～4 weight parts.
3. universal ship bottom antifouling coating according to claim 1 and 2, it is characterized in that, compound organic stain control agent material is: cuprous thiocyanate 5～10 weight parts, Zinc Pyrithione 5～10 weight parts, Seanine 211 molecule titles 4,5-two chloro-2-n-octyls-3-isothiazole copper 2～5 weight parts, two dithio first propylhomoserin zinc 2～5 weight parts of zineb Zineb ethylene.
4. according to the preparation method of each described universal ship bottom antifouling coating among the claim 1-3, may further comprise the steps:
Zinc acrylate resin all is dissolved in the mixed solvent, and fully dissolving adds compound organic stain control agent, dispersion agent, face, filler, anti-settling agent successively, stirs, high speed dispersion high speed dispersion once more after the grinding; After detecting viscosity, fineness, obtain coating.
5. according to each described universal ship bottom antifouling coating among the claim 1-4, it is characterized in that, general application 3～4 roads during such paint spraying, coating thickness need reach 200～300 μ m, when film thickness reaches specified requirement, can reach effective anti-fouling effect.
6. according to each described universal ship bottom antifouling coating among the claim 1-5, it is characterized in that, can be used for aluminium matter, steel substrate surface and waterline position, can in 1-2, effectively prevent marine life stained to hull bottom.
Priority Applications (1)
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| CNA2008100888629A CN101550306A (en) | 2008-04-02 | 2008-04-02 | Universal ship bottom antifouling coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100888629A CN101550306A (en) | 2008-04-02 | 2008-04-02 | Universal ship bottom antifouling coating |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819986A (en) * | 2014-02-08 | 2014-05-28 | 荣成市泓远化工有限公司 | Gray marine antifouling paint without copper compound and preparation method of gray marine antifouling paint |
| CN103992447A (en) * | 2014-06-05 | 2014-08-20 | 上海众取化工有限公司 | Synthesis method of zinc acrylate resin |
| CN104231815A (en) * | 2014-09-30 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Functionalized antifouling anticorrosive graphene paint as well as preparation method and painting method thereof |
| CN104610826A (en) * | 2015-01-16 | 2015-05-13 | 中国船舶重工集团公司第七二五研究所 | Hydrolytic self-polishing antifouling zinc acrylate paint and preparation method thereof |
| CN104629567A (en) * | 2015-01-30 | 2015-05-20 | 厦门双瑞船舶涂料有限公司 | Preparation method of anti-cracking zinc acrylate antifouling paint |
| CN104817913A (en) * | 2015-05-15 | 2015-08-05 | 上海海悦涂料有限公司 | Long-acting environment-friendly ship bottom antifouling paint, strippable antifouling paint and ship bottom antifouling treatment method |
| CN104941894A (en) * | 2015-07-13 | 2015-09-30 | 上海金泛斯标识有限公司 | Aluminum profile spraying technology |
| CN105255297A (en) * | 2015-09-28 | 2016-01-20 | 浙江省海洋开发研究院 | Low surface antifouling paint without copper and tin |
| CN105295630A (en) * | 2014-06-12 | 2016-02-03 | 浙江省海洋开发研究院 | Tin-free and copper-free high-activity antifouling paint and preparation method therefor |
| CN105295631A (en) * | 2015-11-18 | 2016-02-03 | 上海大学 | Fluorine-modified zinc acrylate antifouling coating material and preparation method thereof |
| CN106349777A (en) * | 2016-08-25 | 2017-01-25 | 江苏广能重工有限公司 | General-purpose ship bottom antifouling paint |
| CN106366725A (en) * | 2016-08-25 | 2017-02-01 | 江苏广能重工有限公司 | Color antifouling finish paint |
| CN107779020A (en) * | 2017-10-30 | 2018-03-09 | 海南科维功能材料有限公司 | A kind of environmentally friendly fishing net is without copper protective rubber, protective coating and its dip-coating method |
| CN110724424A (en) * | 2019-10-14 | 2020-01-24 | 浙江海洋大学 | Antifouling coating for marine mesh wire and preparation method thereof |
| CN113072850A (en) * | 2021-05-20 | 2021-07-06 | 上海海隆赛能新材料有限公司 | Antifouling paint and preparation method thereof |
| CN113429845A (en) * | 2021-06-05 | 2021-09-24 | 上海涂固安高科技有限公司 | Antifouling paint formula for hull outer plate |
-
2008
- 2008-04-02 CN CNA2008100888629A patent/CN101550306A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819986A (en) * | 2014-02-08 | 2014-05-28 | 荣成市泓远化工有限公司 | Gray marine antifouling paint without copper compound and preparation method of gray marine antifouling paint |
| CN103992447A (en) * | 2014-06-05 | 2014-08-20 | 上海众取化工有限公司 | Synthesis method of zinc acrylate resin |
| CN105295630A (en) * | 2014-06-12 | 2016-02-03 | 浙江省海洋开发研究院 | Tin-free and copper-free high-activity antifouling paint and preparation method therefor |
| CN105295630B (en) * | 2014-06-12 | 2018-04-17 | 浙江省海洋开发研究院 | A kind of Wuxi is without copper high activity anti-fouling paint and preparation method thereof |
| CN104231815A (en) * | 2014-09-30 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Functionalized antifouling anticorrosive graphene paint as well as preparation method and painting method thereof |
| CN104610826A (en) * | 2015-01-16 | 2015-05-13 | 中国船舶重工集团公司第七二五研究所 | Hydrolytic self-polishing antifouling zinc acrylate paint and preparation method thereof |
| CN104610826B (en) * | 2015-01-16 | 2017-06-20 | 中国船舶重工集团公司第七二五研究所 | A kind of hydrolysis-type zinc acrylate resin self polishing copolymer antifouling paint and preparation method thereof |
| CN104629567A (en) * | 2015-01-30 | 2015-05-20 | 厦门双瑞船舶涂料有限公司 | Preparation method of anti-cracking zinc acrylate antifouling paint |
| CN104817913A (en) * | 2015-05-15 | 2015-08-05 | 上海海悦涂料有限公司 | Long-acting environment-friendly ship bottom antifouling paint, strippable antifouling paint and ship bottom antifouling treatment method |
| CN104941894B (en) * | 2015-07-13 | 2017-04-12 | 上海金泛斯标识有限公司 | Aluminum profile spraying technology |
| CN104941894A (en) * | 2015-07-13 | 2015-09-30 | 上海金泛斯标识有限公司 | Aluminum profile spraying technology |
| CN105255297A (en) * | 2015-09-28 | 2016-01-20 | 浙江省海洋开发研究院 | Low surface antifouling paint without copper and tin |
| CN105295631A (en) * | 2015-11-18 | 2016-02-03 | 上海大学 | Fluorine-modified zinc acrylate antifouling coating material and preparation method thereof |
| CN106349777A (en) * | 2016-08-25 | 2017-01-25 | 江苏广能重工有限公司 | General-purpose ship bottom antifouling paint |
| CN106366725A (en) * | 2016-08-25 | 2017-02-01 | 江苏广能重工有限公司 | Color antifouling finish paint |
| CN107779020A (en) * | 2017-10-30 | 2018-03-09 | 海南科维功能材料有限公司 | A kind of environmentally friendly fishing net is without copper protective rubber, protective coating and its dip-coating method |
| CN110724424A (en) * | 2019-10-14 | 2020-01-24 | 浙江海洋大学 | Antifouling coating for marine mesh wire and preparation method thereof |
| CN110724424B (en) * | 2019-10-14 | 2022-03-25 | 浙江海洋大学 | Antifouling coating for marine mesh wire and preparation method thereof |
| CN113072850A (en) * | 2021-05-20 | 2021-07-06 | 上海海隆赛能新材料有限公司 | Antifouling paint and preparation method thereof |
| CN113429845A (en) * | 2021-06-05 | 2021-09-24 | 上海涂固安高科技有限公司 | Antifouling paint formula for hull outer plate |
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Open date: 20091007 |