CN102010639A - Environmentally-friendly marine antifouling coating and preparation method thereof - Google Patents
Environmentally-friendly marine antifouling coating and preparation method thereof Download PDFInfo
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Abstract
The invention provides a marine antifouling coating. The coating comprises a film forming substance, an antifouling agent and a dilute serving as raw material components, wherein the film forming substance is organic silicon modified acrylic resin; and the antifouling agent comprises nano silver, zinc oxide and a pyrithione coordination compound. An environmentally-friendly marine antifouling coating is prepared by taking the organic silicon modified acrylic resin as the film forming substance, a silane coupling agent and polyamide as curing agents and the nano silver, the zinc oxide and the pyrithione coordination compound as composite disinfection anti-alga agents. The organic silicon modified acrylic resin has low surface energy, so that ordinary microorganisms are difficult to be attached to the surface of the resin; simultaneously, the nano silver and the pyrithione coordination compound have good disinfection and bacteriostasis effects and can effectively prevent the adhesion of marine microorganisms. Moreover, the coating provided by the invention does not contain the conventional cuprous oxide and organic tin antifouling agent, so that the environment is protected well.
Description
Technical field
The present invention relates to a kind of marine anti-pollution and decrease coating and preparation method thereof.
Background technology
Marine fouling organism claims marine attaching organism again, is the general name that is grown in hull bottom and marine all facility surface biologicals.Present known fouling organism has kind more than 2000, comprises animal class, plant class and microbiology class etc.China is coastal more than 600 kind of fouling organism, and wherein main fouling organism has barnacle class, moss animalcules, hydra insects, mollusc, shipworm class, seaweeds etc.Because the difference of global ocean envrionment conditions, sea marine organism pollution embodies because of region difference, difference fouling organism kind in the season characteristics different with adhesion amount.Just because of the diversity of marine fouling organism, complicacy, make and prevent and kill off sea marine organism pollution become international a difficult problem and research focus.
Marine biofouling causes great harm to boats and ships and maritime facilities, can cause metallic corrosion to quicken, increase the quality of hull usually, increase running resistance, reduce the speed of a ship or plane, increase fuel consumption, stop up the seawater transport pipe, influence oceanographic instrumentations such as sonar performance, increase adverse consequencess such as maintenance load, increasing working cost.The method that prevents sea marine organism pollution mainly contains the anti-marine biofouling coating (claiming antifouling paint again) of application, electrochemical method, electrolytic seawater method and submarine mechanical cleaning etc.Wherein the anti-marine biofouling coating of application is at present the most effective, most convenient, most economical method.
Traditional anti-marine biofouling coating is by oozing out of stain control agent settled organism to be killed to reach antifouling purpose, it comprises the solvable type antifouling paint of base-material, abrasion type antifouling paint and self polishing copolymer antifouling paint etc., though aspect antifouling, play a role, because the organometallics stain control agent in this class coating more or less pollutes the environment, cause biomutation, destroy the marine ecology balance and bring harm to human beings'health.Along with the enhancing of people to marine environmental protection consciousness, many countries, International Maritime Organizaton expressly forbid the use of traditional marine antifouling coating.Therefore, exploitation low toxicity, nontoxic environmentally friendly anti-marine biofouling coating have become the important research direction of ocean coating.
At present, the approach of development of new low toxicity, nontoxic environmentally friendly anti-marine biofouling coating mainly contains following two aspects: the one, seek antifouling macromolecular material, change the resin properties in the coating, it is not firm that marine organisms are adhered to, as reduce the free energy of coating surface, or change the physical and chemical performance of coatingsurface; The 2nd, seek nontoxic stain control agent, under the prerequisite of not destroying environment, prevent biological attachment.These researchs are mostly started with from biological attachment mechanism, by mimic biology circle, use the method for " close friend " to stop stained.Wherein, low surface energy anti-fouling paint has had multiple product to use for ship pollution prevention because its nontoxic and unique antifouling mechanism more and more comes into one's own; But problems such as it is poor that this type of coating exists with the priming paint matching capacity, and recoatability is bad.
The stain control agent that nontoxic antifouling paint is used should satisfy: effective to fouling organism under finite concentration, and invalid to non-fouling organism; Transformation period weak point in environment, degraded easily can prevent that the biogenic sediment in food chain from arriving poisonous level; Be suitable for suitability for industrialized production, and the nature eubiosis is not had harm; Meet government regulations,, HUMAN HEALTH pollution-free to big G﹠W do not have harm.Existing nontoxic stain control agent is divided into two kinds of the nontoxic stain control agents of natural biological stain control agent and synthetic.At present, also be in the basic theory stage, also have suitable distance from practical application about the research of natural stain control agent.And the nontoxic stain control agent of synthetic all needs to be used with a large amount of Red copper oxide and just has net effect preferably; Yet a large amount of uses of Red copper oxide class stain control agent have caused a large amount of depositions of copper compound in the bay, bay water quality and marine biological environment have been caused have a strong impact on.Red copper oxide class stain control agent will use in restriction in 2012, therefore, must seek a kind of real environmentally friendly marine anti-pollution and decrease coating to solve the marine organisms attachment issue.
Summary of the invention
The objective of the invention is to overcome above the deficiencies in the prior art, provide a kind of environmentally friendly marine anti-pollution to decrease coating and preparation method thereof.
For achieving the above object, it is stain control agent that the present invention adopts nanometer silver and copper pyrithione or pyrithione zine coordination compound, not containing stain control agents such as organotin and Red copper oxide, is film forming matter with the organosilicon modified crylic acid resin, has prepared environmentally friendly marine anti-pollution and has decreased coating.Technical scheme of the present invention is:
A kind of marine anti-pollution decreases coating, it is characterized in that its feed composition comprises filmogen, stain control agent and thinner; Described filmogen is an organosilicon modified crylic acid resin, and described stain control agent comprises nanometer silver, zinc oxide and pyrithione coordination compound; Gross weight in coating, the weight percentage of described organosilicon modified crylic acid resin is 35-65%, the weight percentage of described nanometer silver is 0.01-0.3%, the weight percentage of described pyrithione coordination compound is 3-7%, and the weight percentage of described zinc oxide is 10-20%.
Described organosilicon modified crylic acid resin is a class modified resin of being made by the polyacrylate resin of activity hydroxy and the organosilicon oligopolymer reaction that contains activity hydroxy (or alkoxyl group), and its number-average molecular weight is about 3000-10000.As the good promise of Sichuan morning twilight, Changzhou, Jiangsu three wood, the corresponding product that makes a concerted effort in Wujiang, Dongming, Shandong petrochemical industry group produces.
Preferably, in the gross weight of described coating, the weight percentage of described nanometer silver is 0.03-0.09%.
Preferably, described nanometer silver is selected Nano silver solution (being the alcoholic solution of nanometer silver) for use, contains nanometer silver 1-3wt% in the described Nano silver solution.
Preferable, described pyrithione coordination compound is selected from copper pyrithione, Zinc Pyrithione or pyrithione silver.
Further, can also comprise in filler, rust-stabilising pigment, silane coupling agent and the rosin one or more in the above-mentioned coating provided by the present invention.
Described filler can be a silicon-dioxide.In the gross weight of described coating, the weight percentage of described filler is 0.5-1%.
Described rust-stabilising pigment can be a red iron oxide.In the gross weight of described coating, the weight percentage of described rust-stabilising pigment is 9-20%.
Described silane coupling agent is selected from 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, vinyl three ('beta '-methoxy oxyethyl group) silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.In the gross weight of described coating, the weight percentage of described silane coupling agent is 1.5-10%.
In the gross weight of described coating, described rosiny weight percentage is 1-5%.
Preferably, a kind of marine anti-pollution provided by the invention decreases coating, comprises following components in weight percentage content:
Silicon-dioxide 0.5-1%
Silane coupling agent 1.5-10%
Organosilicon modified crylic acid resin 35-60%
Thinner 8-18%
Rosin 1-5%
Nanometer silver 0.01-0.3%
Pyrithione coordination compound 3-7%
Zinc oxide 10-20%
Rust-stabilising pigment 9-20%.
The present invention also further discloses the preparation method that above-mentioned environmentally friendly marine anti-pollution decreases coating, comprise the steps: by proportioning, organosilicon modified crylic acid resin, base-material, zinc oxide, pyrithione coordination compound and rust-stabilising pigment are mixed (in 1200 rev/mins of paint cylinder high speeds, disperseed 30 minutes), then sand milling to fineness less than 50 microns, add auxiliary agent (silane coupling agent and rosin), Nano silver solution and thinner at last and stir, get final product.
The present invention also provides a kind of marine anti-pollution to decrease coating combination material, and its feed composition comprises A component and B component, and described A component is above-mentioned any coating, and described B component comprises following components in weight percentage content:
Polyamide resin 10-70%
γ-An Bingjisanyiyangjiguiwan 0-60%
Thinner 0-30%.
Preferably, described B component comprises following components in weight percentage content:
Polyamide resin 40-70%
γ-An Bingjisanyiyangjiguiwan 0-30%
Thinner 20-30%.
Described polyamide resin is the low molecule pa resin that dimerization vegetable fatty acids and aliphatic amide polycondensation form, and all can adopt as general 650,651,300# polyamide resin.
Preferable, the weight ratio of described A component and B component is 6～9: 1.A component and B component are deposited separately, during use both are mixed by weight to get final product.
Among the present invention, employed thinner includes but not limited to methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, phenylcarbinol, petroleum spirit, hexanaphthene, toluene, dimethylbenzene, naphthalene, methylethylketone, acetone, methyl iso-butyl ketone (MIBK), methyl isoamyl ketone, Pyranton, pimelinketone, butoxy ethanol, propylene glycol monomethyl ether, butyldiglycol, acetate methoxy-propyl ester, ethyl acetate, methyl acetate, butylacetate, acetate-2-ethoxyethyl group ester, methylene dichloride, tetrachloroethane, their mixing of trieline.
The present invention is a filmogen with organosilicon-modified acrylic fat, is solidifying agent with silane coupling agent and polymeric amide, and selecting nanometer silver, zinc oxide and pyrithione coordination compound simultaneously for use is composite bactericidal, anti-algae agent, has prepared environmentally friendly marine anti-pollution and has decreased coating.Organosilicon modified crylic acid resin has low surface energy, and general microorganism one is not easy to be attached to the surface, and nanometer silver and pyrithione coordination compound have the good sterilization bacteriostatic action simultaneously, can effectively stop adhering to of marine microorganism.In addition, do not contain traditional Red copper oxide and the agent of organotin stain control agent in the coating provided by the present invention, can protect environment well.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be understood that these embodiment only are used to illustrate the present invention, but not limit the scope of the invention.
Embodiment 1 content of nanometer silver is the preparation of 0.03% coating
The prescription of component A is as follows:
8 kilograms of silicon-dioxide
20 kilograms of 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicanes
400 kilograms of organosilicon modified crylic acid resins (Jiangsu three wood gum companies, model SM1057)
180 kilograms of dimethylbenzene
17 kilograms of rosin
33 kilograms of the solution of Nano silver solution 1%
35 kilograms of copper pyrithiones
180 kilograms in zinc oxide
150 kilograms of red iron oxides
The prescription of B component is as follows:
40 kilograms of polyamide resins (Jiangsu three wood gum companies, model 650)
30 kilograms of γ-An Bingjisanyiyangjiguiwans
30 kilograms of thinner dimethylbenzene
Preparation method: 400 kilograms of organosilicon modified crylic acid resins, 8 kilograms of silicon-dioxide, 180 kilograms in zinc oxide, 150 kilograms of iron oxide reds, 35 kilograms of copper pyrithiones, thinner are added the paint cylinder for 100 kilograms, 1200 rev/mins at a high speed, disperseed 30 minutes.Back sand milling to fineness less than 50 microns, back paint adds 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, rosin, Nano silver solution, thinner cleans the paint cylinder and uses in the time of sand milling, at last the thinner of polishing remainder.Stir at last and obtain the A component.The preparation of B component: 40 kilograms of polyamide resins, 30 kilograms of γ-An Bingjisanyiyangjiguiwans, thinner are mixed for 30 kilograms and get final product.
Coating is 9 to 1 to mix by A component and B component by weight, and prepares.
Embodiment 2 content of nanometer silver are the preparation of 0.06% coating
The prescription of component A is as follows:
8 kilograms of silicon-dioxide
22 kilograms in vinyl three ('beta '-methoxy oxyethyl group) silane
500 kilograms of organosilicon modified crylic acid resins (the DS-502 resin that Dongming, Shandong petrochemical industry group produces)
100 kilograms of pimelinketone
50 kilograms of Zinc Pyrithione
30 kilograms of rosin
65 kilograms of the solution of Nano silver solution 1%
125 kilograms in zinc oxide
100 kilograms of red iron oxides
The prescription of B component is as follows:
60 kilograms of polyamide resins (Jiangsu three wood gum companies, model 650)
20 kilograms of γ-An Bingjisanyiyangjiguiwans
20 kilograms of dimethylbenzene
Preparation method: 500 kilograms of organosilicon modified crylic acid resins, 0 kilogram of silica 1,125 kilograms in zinc oxide, 100 kilograms of iron oxide reds, 50 kilograms of Zinc Pyrithione, thinner are added the paint cylinder for 60 kilograms, 1200 rev/mins at a high speed, disperseed 30 minutes.Back sand milling to fineness less than 50 microns, back paint adds vinyl three ('beta '-methoxy oxyethyl group) silane, rosin, Nano silver solution, thinner cleans the paint cylinder and uses in the time of sand milling, at last the thinner of polishing remainder.Stir at last and obtain the A component.The preparation of B component: 60 kilograms of polyamide resins, 20 kilograms of γ-An Bingjisanyiyangjiguiwans, thinner are mixed for 20 kilograms and get final product.
Coating is 7.2 to 1 to mix by A component and B component by weight, and prepares.
Embodiment 3 content of nanometer silver are the preparation of 0.09% coating
The prescription of component A is as follows:
0 kilogram of silica 1
30 kilograms of γ-(methacryloxypropyl) propyl trimethoxy silicane
600 kilograms of organosilicon modified crylic acid resins (the limited public affairs of Jiangsu three wood gums, model SMH-30)
100 kilograms of dimethylbenzene
24 kilograms of rosin
31 kilograms of the solution of Nano silver solution 3%
36 kilograms of Zinc Pyrithione
The zinc oxide 105 kg
100 kilograms of red iron oxides
The prescription of B component is as follows:
70 kilograms of polyamide resins (the limited public affairs of Jiangsu three wood gums, model 651)
30 kilograms of thinner dimethylbenzene
Preparation method: 600 kilograms of organosilicon modified crylic acid resins, 0 kilogram of silica 1,125 kilograms in zinc oxide, 100 kilograms of iron oxide reds, 20 kilograms of pyridine sulphur copper silver, thinner are added the paint cylinder for 40 kilograms, 1200 rev/mins at a high speed, disperseed 30 minutes.Back sand milling to fineness less than 50 microns, back paint adds γ-(methacryloxypropyl) propyl trimethoxy silicane and goes into silane, rosin, Nano silver solution, thinner cleans the paint cylinder and uses in the time of sand milling, the thinner of last polishing remainder.Stir at last and obtain the A component.The preparation of B component: 70 kilograms of polyamide resins, thinner are mixed for 30 kilograms and get final product.Coating is 6 to 1 to mix by A component and B component by weight, and prepares
Embodiment 4
Content of nanometer silver is the preparation of 0.03% coating
5 kilograms of silicon-dioxide
15 kilograms of 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicanes
400 kilograms of organosilicon modified crylic acid resins (the limited public affairs of Jiangsu three wood gums, model SM1061A)
180 kilograms of dimethylbenzene
15 kilograms of rosin
30 kilograms of the solution of Nano silver solution 1%
35 kilograms of copper pyrithiones
The zinc oxide 120 kg
200 kilograms of red iron oxides
The preparation method is with the A component among the embodiment 1.
Embodiment 5
Content of nanometer silver is the preparation of 0.06% coating
5 kilograms of silicon-dioxide
15 kilograms of 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicanes
460 kilograms of organosilicon modified crylic acid resins (Jiangsu three wood gum company limiteds, model SM1062)
80 kilograms in acetone
50 kilograms of rosin
60 kilograms of the solution of Nano silver solution 1%
30 kilograms of copper pyrithiones
200 kilograms in zinc oxide
100 kilograms of red iron oxides
The preparation method is with the A component among the embodiment 1.
Embodiment 6
Content of nanometer silver is the preparation of 0.09% coating
5 kilograms of silicon-dioxide
100 kilograms of 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicanes
500 kilograms of organosilicon modified crylic acid resins (Sichuan morning twilight chemical research institute, model GY-209-1)
80 kilograms in acetone
10 kilograms of rosin
30 kilograms of the solution of Nano silver solution 1%
70 kilograms of copper pyrithiones
The zinc oxide 105 kg
100 kilograms of red iron oxides
The preparation method is with the A component among the embodiment 1.
The foregoing description gained coating is experimentized and estimate with reference to the test method of GB GB/T 7789-2007 defined, be 30 days (in April, 2010-May) experimental period, and the result is as shown in table 1:
Table 1
Antifouling paint of the present invention as can be seen from Table 1 has anti-fouling effect preferably, and algae adheres to number average and is less than 5, and area coverage percentage ratio is less than 5%, illustrates that anti-fouling effect is obvious.
In addition, in actual ocean environment the foregoing description gained antifouling paint is tested accordingly, the lacing film model that has applied antifouling paint was soaked in seawater 30 days, the result is as follows:
1. the surperficial blank model of only having brushed pure polyurethane coating soaks 30 days in seawater after, the model surface is covered by marine organisms fully, comprises shellfish, marine alga, sea-tangle etc.
External coating embodiment 1 content of nanometer silver be the model of 0.03% coating, in seawater, soak after 30 days, the model surface also is attached biological the covering, but there is not the shellfish mollusk, have only the marine plant of marine alga and so on to adhere to, illustrate in the coating that the nano-Ag particles that discharges has gradually disturbed the absorption of sea mollusk to nutritive substance to the killing action of marine microorganism, has directly influenced sea mollusk adhering at material surface; External coating embodiment 2 content of nanometer silver be the model of 0.06% coating, in seawater, soak after 30 days, the settled organism on model surface reduces more than embodiment 1; External coating embodiment 3 content of nanometer silver be the model of 0.09% coating, in seawater, soak after 30 days, the model surface is not almost adhered to.
By above-mentioned experiment as can be seen: (1) nanometer silver coating is for the anti-adhesive ability difference of different diatoms, green alga and blue-green algae, and content is 0.06% nanometer silver coating, to investigating the algae kind effectively anti-adhesion effect is arranged all; Nanometer silver concentration is high more, and the restraining effect that algae is adhered to is obvious more.(2) reach 0.09% when content of nanometer silver, the model surface of soaking 30 days in seawater does not almost have marine organisms to adhere to.(3) compare with the common Red copper oxide that needs tens parts of mass percent competence exertions of adding significantly to suppress effect, the acquisition of above-mentioned experimental result only needs the nanometer silver of low concentration.
Above laboratory and ocean environment work place study result show, environmentally friendly marine anti-pollution provided by the invention decreases coating can prevent adhering to of microorganism, and then prevent the corrosion of the microorganism that causes thus.
Claims (10)
1. a marine anti-pollution decreases coating, it is characterized in that, comprises filmogen, stain control agent and thinner; Described filmogen is an organosilicon modified crylic acid resin, and described stain control agent comprises nanometer silver, zinc oxide and pyrithione coordination compound; Gross weight in coating, the weight percentage of described organosilicon modified crylic acid resin is 35-65%, the weight percentage of described nanometer silver is 0.01-0.3%, the weight percentage of described pyrithione coordination compound is 3-7%, and the weight percentage of described zinc oxide is 10-20%.
2. a kind of marine anti-pollution as claimed in claim 1 decreases coating, it is characterized in that described pyrithione coordination compound is selected from copper pyrithione, Zinc Pyrithione or pyrithione silver.
3. a kind of marine anti-pollution as claimed in claim 1 decreases coating, it is characterized in that, also comprises in filler, rust-stabilising pigment, silane coupling agent and the rosin one or more.
4. a kind of marine anti-pollution as claimed in claim 3 decreases coating, it is characterized in that in the gross weight of coating, the weight percentage of described filler is 0.5-1%.
5. a kind of marine anti-pollution as claimed in claim 3 decreases coating, it is characterized in that in the gross weight of coating, the weight percentage of described rust-stabilising pigment is 9-20%.
6. a kind of marine anti-pollution as claimed in claim 3 decreases coating, it is characterized in that in the gross weight of coating, the weight percentage of described silane coupling agent is 1.5-10%.
7. a kind of marine anti-pollution as claimed in claim 6 decreases coating, it is characterized in that, described silane coupling agent is selected from 3-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, vinyl three ('beta '-methoxy oxyethyl group) silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
8. a kind of marine anti-pollution as claimed in claim 3 decreases coating, it is characterized in that in the gross weight of coating, described rosiny weight percentage is 1-5%.
9. a marine anti-pollution decreases coating combination material, it is characterized in that, comprises A component and B component, and described A component is that arbitrary described marine anti-pollution decreases coating among the claim 1-8, and described B component comprises following components in weight percentage content:
Polyamide resin 10-70%
γ-An Bingjisanyiyangjiguiwan 0-60%
Thinner 0-30%.
10. a kind of marine anti-pollution as claimed in claim 9 decreases coating combination material, it is characterized in that the weight ratio of described A component and B component is 6～9: 1.
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