CN101967316A - Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint - Google Patents
Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint Download PDFInfo
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Abstract
The invention discloses a nontoxic antifouling paint for an oceanographic ship and facilities and a method for preparing the paint. The paint consists of the following components in percentage by weight: 15 to 55 percent of base material, 0.01 to 10 percent of antifouling agent, 10 to 30 percent of filler, 0.3 to 25 percent of pigment, 2 to 8 percent of auxiliary agent and 3 to 55 percent of solvent, wherein the antifouling agent is silver grains with average grain diameter of between 1 and 200nm. The paint does not contain toxic agents, such as dichloro-diphenyl-trichloroethane, organic tin, cuprous oxide and the like, at all while effectively suppressing corrosion of marine biological attachments, meets the related regulations of international maritime organization and future development trend of the antifouling paint, realizes non-toxicity and environmental friendliness of the marine antifouling technology, and can be widely applied to the facilities and the fields, such as ships, floating piers, marine oil platforms, submarine cables, cooling pipes of power plant near the sea, sea water culture net cage and the like.
Description
Technical field
The invention belongs to technical field of coatings, particularly a kind of nontoxic antifouling paint that is used for marine ship and facility.
Background technology
One of matter of utmost importance that offshore operation ran into is exactly the part marine organisms adhering to stained various maritime facilitieies such as boats and ships and offshore drilling platform, buoy, net cage for sea farming, hydrospace detection instruments.Tentatively verify at present marine organisms reach 20 surplus ten thousand kinds, wherein settled organism reaches thousands of kinds.These class marine organisms are mainly attached to the position of hull and maritime facilities underwater, can bring very big harm and considerable financial loss to offshore operation, prevent that marine attaching organism from being the focus that people pay close attention to harm and the disadvantageous effect that boats and ships and maritime facilities brought always.
Statistics shows, adheres to relevant material damage with marine organisms and accounts for the 70%-80% that relates to extra large total amount of material with losing efficacy, and stops microorganism significant to the influence of material adherent corrosion effectively.The application antifouling paint is to prevent a kind of not only economy of marine biofouling but also terms of settlement efficiently, the approach that it discharges with certain speed by the marine life toxic agent that will be comprised suppresses halobiontic and adheres to and grow, thereby keeps smooth and coating intact of boats and ships and Offshore Units outside surface.Middle and later periods in last century is organo-tin compound stain control agents such as widespread use tributyltin oxide, three fourths and Tin tetrafluoride., fentin chloride, triphenyl tin fluoride once.Though organotin stain control agent consumption is low, the efficient height, has broad spectrum, yet this class organo-tin compound has teratogenecity, at marine life, as in fish, the shellfish body cumulative function being arranged, not only can cause marine life heritable variation, also food chain be can enter, the heredity and the existence of the mankind and other biological had a strong impact on, thereby later stage in last century various countries' forbidding organotin antifouling paint of making laws one after another.International Maritime Organizaton (IMO) uses this series products from total ban on January 1 in 2008 at boats and ships.After the organic tin antifouling paint was under an embargo and uses, its surrogate mainly was exactly to be main stain control agent, to add the product that other auxiliary antifouling chemical agents constitute again with Red copper oxide.80% marine antifouling coating adopts Red copper oxide as stain control agent now.Although its direct injury to human body is still uncertain at present, the toxicity index of some fish and whale then is greater than 24h.What can not be ignored simultaneously is, the copper compounds separate out and be deposited in the seabed in a large number, algae grows and downstream food chain thereof are brought great threat, will inevitably bring nonvolatil injury and pollution to ocean environment.Therefore, International Maritime Organizaton will begin to limit the use of Red copper oxide in 2012, and Chinese environmental protection general bureau also classifies Red copper oxide as excessive risk, high pollution list, and plans to ban use of in 2012.In view of this, the exploitation of novel nontoxic antifouling coating material is extremely urgent.
A kind of fluorine and/or siloxanes low surface energy anti-fouling paint are disclosed for China Patent No. CN98812901 number.The shortcoming of low surface energy coatings maximum is that the coating that brings of low surface free energy is relatively poor to the sticking power and the sticking power between coat layer of base material, and recoatability is bad, gives execution of coating and repairs and can cause difficulty.China Patent No. CN200510081683 discloses a kind of zinc acrylate resin that contains peppery plain functional group or resin of copper and preparation method thereof.But regrettably, this class coating is subjected to the restriction of processing condition, and also exists suitable distance between practical application, and its large-scale production also is difficult to realize at present.The suitable growth environment of marine fouling organism is the slight alkalinity seawater of pH value for 7.5-8.0, all is difficult for existence in highly basic or highly acid environment.It is the nontoxic antifouling paint of stain control agent with silicate that China Patent No. CN97121813 discloses a kind of.But studies show that the effective antifouling life of alkaline silicate antifouling paint is not long, physicochemical property is poor, and actual application prospect is also uncertain.
Summary of the invention
The objective of the invention is to overcome existing antifouling paint deficiency, a kind of novel non-toxic anti-pollution paint for sea is provided; Another object of the present invention provides the preparation method of this coating.
The objective of the invention is to be achieved through the following technical solutions:
A kind of nontoxic antifouling paint that is used for marine ship and facility, by base-material, stain control agent, filler, pigment, auxiliary agent and solvent composition, the weight percent of described each component is:
Base-material 15～55%,
Stain control agent 0.01～10%,
Filler 10～30%,
Pigment 0.3～25%,
Auxiliary agent 2～8%,
Solvent 3～55%.
Described stain control agent is the silver-colored particle of median size rice in 1～200.
In the above-mentioned antifouling paint, described base-material is at least a in acrylic resin, ethenoid resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, pitch, poly divinyl acetylene resin, resol, urea-formaldehyde resin, melamine resin, urethane, Resins, epoxy, Synolac, silicone resin, organic fluorine or the subsilicate.
In the above-mentioned antifouling paint, described filler is at least a in lime carbonate, barium carbonate, silicon-dioxide, talcum powder, graphite, zinc oxide, diatomite, glass microsphere, ground barium sulfate, wilkinite, organic pottery clay, china clay, zeolite powder or the mica.
In the above-mentioned antifouling paint, described pigment is at least a in red iron oxide, laterite, iron oxide yellow, carbon black, titanium dioxide, zinc sulfide white, magnesium oxide, barba hispanica, ultramarine, diarylide yellow, calcium phosphate, trimagnesium phosphate or the barium metaborate.
In the above-mentioned antifouling paint, described auxiliary agent is at least a in dispersion agent, defoamer, flow agent, film coalescence aid, wetting agent, softening agent, siccative, pH regulator agent, sanitas, anti-heavy and the thixotropic thickening agent;
Above-mentioned auxiliary agent can be selected from but be not limited to following kind:
Dispersion agent: Sodium hexametaphosphate 99, Sodium dodecylbenzene sulfonate, Zinic stearas, Yelkin TTS, Disper BYK series;
Defoamer: tributyl phosphate, dimethyl polysiloxane, polyether-modified methyl polysiloxane, aluminum stearate;
Flow agent: polymethyl acrylate, PSI, polyester modification polydimethyl silane;
Film coalescence aid: alcohol ester 12, Texanol, ethylene glycol, sherwood oil, diisobutyl adipic acid ester;
Wetting agent: vinyltriethoxysilane, vinyltriacetoxy silane, dimethyl silicone oil;
Softening agent: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, Viscotrol C, clorafin;
Siccative: cobalt naphthenate, manganese naphthenate, calcium iso-octoate, zirconium iso-octoate, diethyl are with sour cobalt;
Sanitas: Sodium Benzoate, isothiazolinone, benzisothiazole ketone (BIT);
PH regulator agent: ammoniacal liquor, aqueous sodium hydroxide solution, acetate;
Anti-heavy and thixotropic thickening agent: organobentonite, aluminium octoate, calcium stearate, polyethylene wax, zinc ricinate.
In the above-mentioned antifouling paint, described solvent is a ketone, for example acetone, pimelinketone, butanone or ester class, for example ethyl acetate, butylacetate or jasmal; Alcohols, for example methyl alcohol, ethanol, Virahol, isopropylcarbinol, ethylene glycol or propylene glycol; Ethers, for example ethylene glycol ethyl ether, butyl glycol ether or propylene-glycol ethyl ether; Fat hydrocarbon, for example normal hexane, hexanaphthene, Skellysolve A, octane or heptane; Arene, for example at least a in toluene, dimethylbenzene, trimethylbenzene or the water.
A kind of method for preparing above-mentioned antifouling paint, it carries out according to the following steps:
Under the condition of room temperature to 80 ℃, base-material added in the solvent dissolves, add stain control agent, pigment, filler and auxiliary agent successively, stir, disperse, grind 2～6 hours with the rotating speed of 1500～5000r/min after, make antifouling paint.
The present invention utilizes silver-colored particle that human body and other organism are had no side effect, have broad spectrum antibacterial and eco-friendly characteristics, development is used for the nontoxic antifouling paint of marine ship and facility, when effectively suppressing the marine organisms adherent corrosion, do not contain toxic agent such as dichlorodiphenyl trichloroethane (DDT), organotin (TBT), Red copper oxide fully, the future development trend that meets International Maritime Organizaton's (IMO) relevant regulations and antifouling paint has realized that the nothing of marine anti-pollution technology poisons and greenization.
Compared with prior art, the present invention has following outstanding advantage:
1. yardstick is that the silver-colored particle of 1～200 nanometer is used to prepare ocean coating, and antifouling property is remarkable, is the tool anti-fouling effect under lower concentration, and the cost performance height;
2. antifouling paint of the present invention has the antifouling usefulness of wide spectrum to adhering to marine organisms;
3. antifouling paint of the present invention in use can not discharge toxic substance, environmental protection in seawater;
4. antifouling paint of the present invention can be widely used in boats and ships, floating terminal, offshore platform, undersea cable, border on the sea facility and fields such as power station cooling duct and net cage for sea farming.
Embodiment
Below in conjunction with embodiment, technology of the present invention and characteristics are described further.
Embodiment 1
Each component is joined in the multi-functional dispersion machine material-compound tank by following prescription, and mixture remains under 50 ℃, stirs, disperses, grinds 4 hours with the rotating speed of 2000r/min, makes 1kg non-toxic anti-pollution paint for sea finished product.
Each composition weight is respectively in the prescription:
(1) acrylic resin 500.00g,
(2) zinc oxide 187.43g,
(3) red iron oxide 124.95g,
(4) talcum powder 62.57g,
(5) dimethylbenzene 124.95g,
(6) silver-colored particle 0.10g,
Described silver-colored particulate median size is 15nm.
Embodiment 2
(1) water soluble acrylic resin's base-material and water are mixed into the water soluble resin aqueous solution, in the water soluble resin aqueous solution, add organo-silicon coupling agent vinyltriethoxysilane and dimethyl-silicon oil assistant then;
(2) under 55 ℃ of conditions, superfine silicon dioxide, titanium dioxide, zinc oxide, light magnesium oxide, water glass and stain control agent are added in the multi-functional dispersion machine material-compound tank successively; Rotating speed with 3500r/min stirs, disperses, ground 2 hours, makes the 1kg non-toxic anti-pollution paint for sea.
Each composition weight is respectively in the prescription:
(1) water soluble acrylic resin 392.04g,
(2) deionized water 417.00g,
(3) vinyltriethoxysilane 6.58g,
(4) dimethyl silicone oil 16.06g,
(5) superfine silicon dioxide 22.94g,
(6) titanium dioxide 13.28g,
(7) zinc oxide 45.96g,
(8) light magnesium oxide 32.70g,
(9) water glass 52.44g,
(10) silver-colored particle 1.00g,
Described silver-colored particulate median size is about 1nm.
Embodiment 3
Each component is joined in the multi-functional dispersion machine material-compound tank by following prescription, and mixture keeps at room temperature, stirs, disperses, grinds 6 hours with the rotating speed of 1500r/min, makes 1kg non-toxic anti-pollution paint for sea finished product.
Each composition weight is respectively in the prescription:
(1) coal coke asphalt liquid 90.82g,
(2) rosin 208.58g,
(3) zinc oxide 159.68g,
(4) laterite 211.58g,
(5) talcum powder 93.81g,
(6) heavy benzene 233.53g,
(7) silver-colored particle 2.00g,
Described silver-colored particulate median size is 22nm.
Embodiment 4
Each component is joined in the multi-functional dispersion machine material-compound tank by following prescription, and mixture remains under 40 ℃, stirs, disperses, grinds 3 hours with the rotating speed of 5000r/min, makes 1kg non-toxic anti-pollution paint for sea finished product.
Each composition weight is respectively in the prescription:
(1) ethenoid resin 149.25g
(2) tributyl phosphate 27.26g,
(3) rosin 113.76g,
(4) Resins, epoxy 3.28g,
(5) laterite 236.91g,
(6) zinc oxide 165.87g,
(7) talcum powder 94.72g,
(8) organic pottery clay 11.84g,
(9) pimelinketone 85.57g,
(10) trimethylbenzene 106.57g,
(11) silver-colored particle 4.97g,
Described silver-colored particulate median size is 45nm.
Embodiment 5
Each component is joined in the multi-functional dispersion machine material-compound tank by following prescription, and mixture remains under 80 ℃, stirs, disperses, grinds 2 hours with the rotating speed of 4000r/min, makes 1kg non-toxic anti-pollution paint for sea finished product.
Each composition weight is respectively in the prescription:
(1) 35% chlorinated rubber liquid 99.58g,
(2) clorafin 28.96g,
(3) 50% carboxylic ester 34.77g,
(4) rosin 104.32g,
(5) laterite 231.77g,
(6) zinc oxide 162.23g,
(7) talcum powder 92.69g,
(8) organic pottery clay 11.62g,
(9) barium meta carbonate 11.62g,
(10) dimethylbenzene 214.94g,
(11) silver-colored particle 7.50g,
Described silver-colored particulate median size is 64nm.
Embodiment 6
Each component is joined in the multi-functional dispersion machine material-compound tank according to this by following prescription, and mixture remains under 50 ℃, stirs, disperses, grinds 4 hours with the rotating speed of 2500r/min, and regulating the pH value with sodium hydroxide is 8.Make 1kg non-toxic anti-pollution paint for sea finished product.
Each composition weight is respectively in the prescription:
(1) organosilicon crylic acid latex 554.26g,
(2) Sodium hexametaphosphate 99 27.74g,
(3) zinc oxide 269.50g,
(4) Natvosol 13.77g,
(5) tributyl phosphate 1.36g,
(6) Sodium Benzoate 2.82g,
(7) ethylene glycol 27.74g,
(8) propylene glycol 2.81g,
(9) silver-colored particle 100.00g,
Described silver-colored particulate median size is 78nm.
Embodiment 7
Acrylic resin is dissolved in the mixed solvent, adds silver-colored particle, dispersion agent, pigment, filler etc. successively, remain under 35 ℃, stir, disperse, ground 2.5 hours, make 1kg non-toxic anti-pollution paint for sea finished product with the 3000r/min rotating speed.
Each composition weight is respectively in the prescription:
(1) acrylic resin 435.86g,
(2) talcum powder 43.51g,
(3) zinc oxide 145.26g,
(4) phthalocyanine blue 2.94g,
(5)Disper?BYK?102 2.94g，
(6) organobentonite 32.07g,
(7) dimethylbenzene 226.84g,
(8) butylacetate 72.58g,
(9) silver-colored particle 38.00g,
Described silver-colored particulate median size is 126nm.
Embodiment 8
Modified organic silicon is dissolved in the organic solvent, add successively again auxiliary agent, silver-colored particles such as clorafin, zinc oxide, dimethyl silicone oil, fluorocarbon surfactants, remain under 65 ℃, stir, disperse, ground 3.5 hours with the 1800r/min rotating speed, become low surface energy non-toxic anti-pollution paint for sea A component.At room temperature, low molecular polyamides is dissolved in makes antifouling paint B component in the mixed solvent.Before use two components of A, B are mixed.
Each composition weight is respectively in the prescription:
The A component:
(1) modified organic silicon 287.40g,
(2) clorafin 67.06g,
(3) zinc oxide 38.32g,
(4) fluorocarbon surfactant 2.50g,
(5) dimethyl silicone oil 3.25g,
(5) mixed solvent 496.24g,
(6) silver-colored particle 42.00g,
The B component:
(1) low molecular polyamides 5.75g,
(2) mixed solvent 57.48g,
Described mixed solvent is the mixture of toluene, dimethylbenzene, propyl carbinol, isopropylcarbinol and Virahol.
Described silver-colored particulate median size is 200nm.
The above only is a preferred implementation of the present invention, should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise, can also make some improvement and change and also should be considered within the scope of protection of the present invention.
Claims (7)
1. nontoxic antifouling paint that is used for marine ship and facility, it is by base-material, stain control agent, filler, pigment, auxiliary agent and solvent composition, it is characterized in that described stain control agent is the silver-colored particle of median size rice in 1～200, the weight percent of described each component is:
Base-material 15～55%,
Stain control agent 0.01～10%,
Filler 10～30%,
Pigment 0.3～25%,
Auxiliary agent 2～8%,
Solvent 3～55%.
2. nontoxic antifouling paint according to claim 1, it is characterized in that described base-material is at least a in acrylic resin, ethenoid resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, pitch, poly divinyl acetylene resin, resol, urea-formaldehyde resin, melamine resin, urethane, Resins, epoxy, Synolac, silicone resin, organic fluorine or the subsilicate.
3. nontoxic antifouling paint according to claim 2, it is characterized in that described filler is at least a in lime carbonate, barium carbonate, silicon-dioxide, talcum powder, graphite, zinc oxide, diatomite, glass microsphere, ground barium sulfate, wilkinite, organic pottery clay, china clay, laterite, zeolite powder or the mica.
4. nontoxic antifouling paint according to claim 3, it is characterized in that described pigment is at least a in red iron oxide, iron oxide yellow, carbon black, titanium oxide, zinc sulfide white, magnesium oxide, barba hispanica, ultramarine, diarylide yellow, calcium phosphate, trimagnesium phosphate or the barium metaborate.
5. nontoxic antifouling paint according to claim 4, it is characterized in that described auxiliary agent is at least a in dispersion agent, defoamer, flow agent, film coalescence aid, wetting agent, softening agent, siccative, pH regulator agent, sanitas or anti-heavy and the thixotropic thickening agent; Wherein,
Described dispersion agent is: Sodium hexametaphosphate 99, Sodium dodecylbenzene sulfonate, Zinic stearas, Yelkin TTS;
Described defoamer is: tributyl phosphate, dimethyl polysiloxane, polyether-modified methyl polysiloxane, aluminum stearate;
Described flow agent is: polymethyl acrylate, PSI, polyester modification polydimethyl silane;
Described film coalescence aid is: alcohol ester 12, Texanol, ethylene glycol, sherwood oil, diisobutyl adipic acid ester;
Described wetting agent is: vinyltriethoxysilane, vinyltriacetoxy silane, dimethyl silicone oil;
Described softening agent is: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, Viscotrol C;
Described siccative is: cobalt naphthenate, manganese naphthenate, calcium iso-octoate, zirconium iso-octoate, diethyl are with sour cobalt;
Described sanitas is: Sodium Benzoate, isothiazolinone, benzisothiazole ketone (BIT);
Described pH regulator agent is: ammoniacal liquor, aqueous sodium hydroxide solution, acetate;
Described anti-sinking with thixotropic thickening agent is: organobentonite, aluminium octoate, calcium stearate, polyethylene wax, zinc ricinate.
6. nontoxic antifouling paint according to claim 5 is characterized in that, described solvent is a ketone, is specially: acetone, pimelinketone, butanone; The ester class is specially: ethyl acetate, butylacetate, jasmal; Alcohols is specially: methyl alcohol, ethanol, Virahol, isopropylcarbinol, ethylene glycol, propylene glycol; Ethers is specially: ethylene glycol ethyl ether, butyl glycol ether, propylene-glycol ethyl ether; Fat hydrocarbon is specially: normal hexane, hexanaphthene, Skellysolve A, octane, heptane; Arene is specially: at least a in toluene, dimethylbenzene, trimethylbenzene or the water.
7. one kind prepares as being used for the method for the nontoxic antifouling paint of marine ship and facility as described in the claim 1,2,3,4,5 or 6, it is characterized in that it carries out according to the following steps:
Under the condition of room temperature to 80 ℃, base-material added in the solvent dissolves, add stain control agent, pigment, filler and auxiliary agent successively, stir, disperse, grind 2～6 hours with the rotating speed of 1500～5000r/min after, make described nontoxic antifouling paint.
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