CN102337063A - Preparation method of low-surface-energy ship antifouling paint capable of releasing silicone oil, paint and construction method - Google Patents
Preparation method of low-surface-energy ship antifouling paint capable of releasing silicone oil, paint and construction method Download PDFInfo
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Abstract
The invention discloses a preparation method of low-surface-energy ship antifouling paint capable of releasing silicone oil. The preparation method comprises the following steps: 1) preparing a raw material in advance; and 2) preparing the paint. The invention also discloses paint for implementing the preparation method of the low-surface-energy ship antifouling paint capable of releasing the silicone oil and a construction method for applying the paint. The method provided by the invention has simple preparation process and has high production efficiency, and is easy to realize; the surface energy of the paint provided by the invention is low, the silicon oil releasing speed is slow, and the antifouling property can be maintained for a long time under the condition of the same coating thickness, thereby reducing the maintenance cost of a ship antifouling coating; the VOC (volatile organic compound) content of the antifouling paint is low, thereby reducing atmosphere pollution; and the coating releases low-toxicity silicone oil, thereby lowering the pollution on marine environment. The construction method provided by the invention is simple and has low cost; and by using the construction method, the antifouling function of the paint is effectively exerted.
Description
Technical field
The invention belongs to the marine ship antifouling paint, be specifically related to a kind of low surface energy anti-fouling ship paint preparation method, coating and constructional method that can discharge silicone oil.
Background technology
Boats and ships are important channels of international staple commodities transportation, and in ocean environment, boats and ships can receive sea-water corrosion, also receive adhering to of marine microorganism simultaneously and the biological pollution that causes.According to statistics, many kinds of marine fouling organisms of 2000-3000 are arranged in the marine site all over the world, wherein about 600 kinds of attached plants and 1300 kinds of epizoites; Larva of these mikrobes and spore be floating in the ocean, move about, and grows to a certain degree when it and can adhere to alow, settle down and further breeding, after boats and ships adhere to marine life; Can cause surface friction drag to increase; Reduce ship's speed, increase fuel consumption, increase the frequency of maintenance that lies up.
For preventing that sea life from adhering to, effective means is at shell surface-coated antifouling paint.In decades in the past, the antifouling paint that contains organotin is once by a large amount of uses.But disengage thing sea life have been caused teratogenesis and secular Marine Environmental Pollution.Therefore, from January 1st, 2008, Marine Environmental Protection Committee (MEPC) completely forbade use.At present, the substitute is the less hypotoxic stain control agents such as Red copper oxide of toxicity.But the result shows according to current research, and the halobiontic kind reduction of some International Ports and the minimizing of living weight and the use of copper class stain control agent have very big relation.Therefore, the exploitation hypotoxicity antifouling paint that disengages thing, low surface energy becomes main solution.
At present, the antifouling paint that has a low surface energy constantly is developed.Chinese patent CN1498252A has described a kind of antifouling paint compositions, comprising PFPE, silicone resin, solidifying agent etc.This coating composition has low surface energy, only relies on low surface energy to reach and reduces biological adhering to, and in the marine low speed operation, when length of port stay is longer, its anti-fouling effect is difficult to guarantee.
Chinese patent CN1492010A has described a kind of by fluoro-acrylate monomer, vinylformic acid three organic radical silyl ester monomers, acrylic monomer polymeric multipolymer; And utilize this multipolymer as film forming matter, cooperate Red copper oxide and red stone etc. to be mixed with antifouling paint.Through regulating monomeric proportioning, multipolymer has 1～200 micron/month etch rates.The characteristic that this coating has low surface energy, polishes certainly have good application prospects, but this coating contains the Red copper oxide stain control agent, still ocean environment is had potential danger, destructiveness, and ejecta is very difficult by biological degradation, and the residence time is long.
Summary of the invention
To above-mentioned deficiency, one of the object of the invention is, provides a kind of technology simple and easy, the low surface energy anti-fouling ship paint preparation method that can discharge silicone oil who is easy to produce;
Two of the object of the invention is; A kind of above-mentioned coating that can discharge the low surface energy anti-fouling ship paint preparation method of silicone oil of implementing is provided; This coating utilizes the didirtresistance of its low surface energy, slowly discharge silicone oil reduces biological tack and reaches dual anti-fouling effect, and this double effects is given coating good antifouling performance.
Three of the object of the invention is, a kind of constructional method of implementing above-mentioned coating is provided.
For realizing above-mentioned purpose, technical scheme provided by the present invention is:
A kind of low surface energy anti-fouling ship paint preparation method that can discharge silicone oil is characterized in that it may further comprise the steps:
(1) preparing material: each component and the weight percentage thereof of coating are following:
Fluorine silicon vinyl resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Said powder is for include a kind of in silicon-dioxide, aluminum oxide, the titanium oxide at least;
Said solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, MIBK, MIPK, methyl n-butyl ketone, MIBK, the THF two or more;
Catalyzer is an organotin catalysts.
(2) preparation coating: fluorine silicon vinyl resin, powder, silicone oil, solvent, catalyzer, dispersion agent, the anti-sagging agent of corresponding proportional quantity are carried out dispersing and mixing, make coating.
The preparation method of the fluorine silicon vinyl resin in the described step (1) specifically comprises the steps:
(1.1) preparation first mixing solutions: the weight percentage of first mixing solutions is 5～30%, in YLENE, adds N-BUTYL ACETATE, and uniform mixing makes first mixing solutions; The weight percentage of YLENE in first mixing solutions is 30～70%;
(1.2) preparation second mixing solutions: prepare the raw material of second mixing solutions, each component and the weight percentage thereof of this raw material are following:
TEB 3K 20～50%;
Bing Xisuandingzhi 10～20%;
Rocryl 400 3～10%;
Initiator 0.5～5%;
The mixing solutions 3～20% of fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate,
The mixing solutions of TEB 3K, Bing Xisuandingzhi, Rocryl 400, initiator, fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate of corresponding proportional quantity is carried out uniform mixing make second mixing solutions; The weight percentage of fluorine-containing (methyl) propenoate in the mixing solutions of fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate is 20～80%.
(1.3) drip mixing: first mixing solutions is heated, when being warmed up to 60～100 ℃, slowly be added dropwise to second mixing solutions, until dropwising;
(1.4) insulation: after dropwising, constant temperature kept 2～20 hours, made the fluorine silicon vinyl resin.
The median size of the powder in the described step (1) is 20～1000nm;
The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the ZGK 5 that amino ZGK 5, ZGK 5, YSR 3286, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.Said dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S; Said anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Described step (2), it specifically comprises the steps:
(2.1) preparation A component: by corresponding proportional quantity fluorine silicon vinyl resin, silicone oil, anti-sagging agent are mixed, and add and have in the whisking appliance of TM, mix down at 35～45 ℃ and stirred 25～35 minutes, make the A component;
More than the quality percentage composition of each component in coating be:
Fluorine silicon vinyl resin 15～50%;
Silicone oil 5～30%;
Anti-sagging agent 0.2～2%,
(2.2) preparation B component: press corresponding proportional quantity with powder, dispersion agent, solvent, catalyst mix, and be transferred in the shredder, start shredder, the speed setting of this shredder is 900～1100 rev/mins, and grinding jitter time is 110～250 minutes;
More than the quality percentage composition of each component in coating be:
Powder 30～20%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
(2.3) A component and B component are mixed, and at room temperature stirred 110～250 minutes, make coating.
A kind of coating of implementing the above-mentioned low surface energy anti-fouling ship paint preparation method preparation that can discharge silicone oil is characterized in that its each component and weight percentage thereof are following:
Fluorine silicon vinyl resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Said powder is for include a kind of in silicon-dioxide, aluminum oxide, the titanium oxide at least;
Solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, MIBK, MIPK, methyl n-butyl ketone, MIBK, the THF two or more;
Said catalyzer is an organotin catalysts;
The median size of said powder is 20～1000nm; The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the ZGK 5 that amino ZGK 5, ZGK 5, YSR 3286, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.Said dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S; Said anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Said flaky material is that sericite or the talcum powder of 1～10 μ m processed by particle size diameter.
A kind of constructional method of implementing above-mentioned coating is characterized in that it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness handled;
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and this steel anti-corrosion primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 45～80 μ m;
3) the preparation intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 140～210 μ m;
4) coating evenly is coated on the middle layer, forming thickness is the top coat layer of 230～320 μ m.
Described steel anti-corrosion primer is a kind of in epoxy zinc rich primer, zinc-rich coating, the thick modified epoxy slurry lacquer, and thickness is 45～80 μ m.
Described intermediate coat is epoxy micaceous iron intermediate coat or acrylic polyurethane coating.
Beneficial effect of the present invention is: the preparation technology of method provided by the invention is simple and easy, be easy to realize that production efficiency is high; The surface energy of coating provided by the invention is low, and the silicone oil release rate is slow, under the condition of same coat-thickness, can keep antifouling property more muchly, has reduced the maintenance cost of marine antifouling coating; And the VOC content of antifouling paint is low, has reduced air environmental pollution, and what coating discharged is hypotoxic silicone oil, has reduced the pollution to ocean environment.Constructional method provided by the invention is simple, and cost is low, can make coating effectively give play to its anti-pollution function.
Below in conjunction with accompanying drawing and embodiment, the present invention is described further.
Description of drawings
Fig. 1 is preparation flow figure of the present invention.
Embodiment
Embodiment 1: referring to Fig. 1,
A kind of low surface energy anti-fouling ship paint preparation method that can discharge silicone oil, it may further comprise the steps:
(1) preparing material: each component and the weight percentage thereof of coating are following:
Fluorine silicon vinyl resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Said powder is for include a kind of in silicon-dioxide, aluminum oxide, the titanium oxide at least;
Said solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, MIBK, MIPK, methyl n-butyl ketone, MIBK, the THF two or more;
Catalyzer is an organotin catalysts;
Dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S.
Anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Wherein the preparation method of fluorine silicon vinyl resin specifically comprises the steps:
(1.1) preparation first mixing solutions: the weight percentage of first mixing solutions is 5～30%, in YLENE, adds N-BUTYL ACETATE, and uniform mixing makes first mixing solutions; The weight percentage of YLENE in first mixing solutions is 30～70%;
(1.2) preparation second mixing solutions: prepare the raw material of second mixing solutions, each component and the weight percentage thereof of this raw material are following:
TEB 3K 20～50%;
Bing Xisuandingzhi 10～20%;
Rocryl 400 3～10%;
Initiator 0.5～5%;
The mixing solutions 3～20% of fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate,
The mixing solutions of TEB 3K, Bing Xisuandingzhi, Rocryl 400, initiator, fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate of corresponding proportional quantity is carried out uniform mixing make second mixing solutions; The weight percentage of fluorine-containing (methyl) propenoate in the mixing solutions of fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate is 20～80%.
(1.3) drip mixing: first mixing solutions is heated, when being warmed up to 60～100 ℃, slowly be added dropwise to second mixing solutions, until dropwising;
(1.4) insulation: after dropwising, constant temperature kept 2～20 hours, made the fluorine silicon vinyl resin.
The median size of described powder is 20～1000nm;
The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the ZGK 5 that amino ZGK 5, ZGK 5, YSR 3286, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.
(2) preparation coating: fluorine silicon vinyl resin, powder, silicone oil, solvent, catalyzer, dispersion agent, the anti-sagging agent of corresponding proportional quantity are carried out dispersing and mixing, make coating.
The described low surface energy anti-fouling ship paint preparation method that can discharge silicone oil, described step (2), it specifically comprises the steps:
(2.1) preparation A component: by corresponding proportional quantity fluorine silicon vinyl resin, silicone oil, anti-sagging agent are mixed, and add and have in the whisking appliance of TM, mix down at 35～45 ℃ and stirred 25～35 minutes, make the A component;
More than the quality percentage composition of each component in coating be:
Fluorine silicon vinyl resin 15～50%;
Silicone oil 5～30%;
Anti-sagging agent 0.2～2%,
(2.2) preparation B component: press corresponding proportional quantity with powder, dispersion agent, solvent, catalyst mix, and be transferred in the shredder, start shredder, the speed setting of this shredder is 900～1100 rev/mins, and grinding jitter time is 110～250 minutes;
More than the quality percentage composition of each component in coating be:
Powder 30～20%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
(2.3) A component and B component are mixed, and at room temperature stirred 110～250 minutes, make coating.
A kind of coating of implementing the above-mentioned low surface energy anti-fouling ship paint preparation method preparation that can discharge silicone oil, its each component and weight percentage thereof are following:
Fluorine silicon vinyl resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Said powder is for include a kind of in silicon-dioxide, aluminum oxide, the titanium oxide at least;
Solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, MIBK, MIPK, methyl n-butyl ketone, MIBK, the THF two or more;
Said catalyzer is an organotin catalysts.
The median size of the powder in the described coating is 20～1000nm; The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the ZGK 5 that amino ZGK 5, ZGK 5, YSR 3286, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.
Dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S.
Anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Said flaky material is that sericite or the talcum powder of 1～10 μ m processed by particle size diameter.
A kind of constructional method of implementing above-mentioned coating, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness handled;
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and this steel anti-corrosion primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 45～80 μ m;
3) the preparation intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 140～210 μ m;
4) coating evenly is coated on the middle layer, forming thickness is the top coat layer of 230～320 μ m.
Described steel anti-corrosion primer is a kind of in epoxy zinc rich primer, zinc-rich coating, the thick modified epoxy slurry lacquer, and thickness is 45～80 μ m;
Described intermediate coat is epoxy micaceous iron intermediate coat or acrylic polyurethane coating.
Embodiment 2, and low surface energy anti-fouling ship paint preparation method, coating and the constructional method that can discharge silicone oil are following:
The A component: taking by weighing fluorine silicon vinyl resin 235g, YLENE 20g, THF 30g, hydroxy silicon oil 220g, BYK-430 is 4.8g, adds to have in the whisking appliance of TM, 40 ℃ of mixed down stirrings 0.5 hours.
B component: take by weighing nano silica powder 75g, join and consist of BYK-140 reagent 5g, in the miscellany of YLENE 60g, THF 45g, N-BUTYL ACETATE 40g, dibutyl tin laurate 2.2g.In shredder,, grind and disperseed 3 hours with 1000 rev/mins of rotating speeds.
During use, A component and B component are mixed, stirring at room 120 minutes can be used.
The execution of coating method, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness handled; The surface of steel plate degree of cleaning reach the Sa2 of GB/T 8923-1988 regulation
1/
2Level.
2) preparation has good sticking power and the epoxy zinc rich primer that plays rust inhibition to the surface of steel, epoxy zinc rich primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 50 μ m;
3) preparation epoxy micaceous iron intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 200 μ m;
4) coating of the present invention evenly is coated on the middle layer, forming thickness is the top coat layer of 350 μ m.
Drying conditions is 25 ℃, 50% relative humidity, and be 7 days time of drying, makes the marine antifouling coating.
Embodiment 3: the distinctive points of itself and embodiment 2 is following:
Each components contents and preparation method are following in the coating:
A component: fluorine silicon vinyl resin 280g, YLENE 60g, THF 30g, N-BUTYL ACETATE 50g, dimethyl silicone oil 350g, dibutyl tin laurate 3 grams are mixed.Add and have in the whisking appliance of TM mixed the stirring 0.5 hour under 40 ℃.
B component: at room temperature; Take by weighing 100g nano-titanium dioxide powder, 5g BYK-323, with the mixed solvent and the 3.5g BYK-163 of 60g YLENE, 45g THF, 40g N-BUTYL ACETATE composition, in shredder; With 1200 rev/mins of rotating speeds, grind and disperseed 4 hours.
During use, A component and B component are mixed, room temperature is powerful to be stirred 2 hours, can use.
The execution of coating method, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness handled; The surface of steel plate degree of cleaning reach the Sa2 of GB/T 8923-1988 regulation
1/
2Level.
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and thick modified epoxy slurry lacquer evenly is coated on the surface of steel, and forming thickness is the prime coat of 50 μ m;
3) the preparation acrylic polyurethane coating evenly is coated in it on prime coat, and forming thickness is the middle layer of 200 μ m;
4) coating of the present invention evenly is coated on the middle layer, forming thickness is the top coat layer of 300 μ m.
Drying conditions is 25 ℃, 50% relative humidity, and be 7 days time of drying, makes the marine antifouling coating.
Embodiment 4: the distinctive points of itself and embodiment 2 is following:
Each components contents and preparation method are following in the coating:
The A component: taking by weighing fluorine silicon vinyl resin 1020g, YLENE 110g, THF 80g, hydroxy silicon oil 800g, BYK-323 is 20g, adds to have in the whisking appliance of TM, 40 ℃ of mixed down stirrings 0.5 hours.
B component: take by weighing nano silica powder 300g, join and consist of BYK-140S reagent 22g, in the miscellany of YLENE 210g, THF 180g, N-BUTYL ACETATE 140g, dibutyl tin laurate 8g.In shredder,, grind and disperseed 3 hours with 1000 rev/mins of rotating speeds.
During use, A component and B component are mixed, stirring at room 2 hours can be used.
The execution of coating method, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness handled; The surface of steel plate degree of cleaning reach the Sa2 of GB/T 8923-1988 regulation
1/
2Level.
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, zinc-rich coating evenly is coated on the surface of steel, and forming thickness is the prime coat of 80 μ m;
3) preparation epoxy micaceous iron intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 150 μ m;
4) coating according to the invention evenly is coated on the middle layer, forming thickness is the top coat layer of 400 μ m.
Drying conditions is 25 ℃, 50% relative humidity, and be 7 days time of drying, makes the marine antifouling coating.
Table 1 is to adopt resultant finish paint coating process of the above embodiment of the present invention and physico-chemical parameter, and concrete parameter is following:
Table 1: embodiment finish paint performance perameter
Can find out that through the performance index in the table 1 because the surface energy of coating is low, utilize the didirtresistance of the low surface energy of coating, slowly discharge silicone oil and reduce biological tack and reach dual anti-fouling effect, this double effects is given coating good antifouling performance.This coating system matrix resin is the fluorine silicon vinyl resin, has low surface energy; It is silicone oil that coating is disengaged thing, and it has low toxicity, the slow characteristics of release rate.This coating has longer antifouling phase, better didirtresistance, low VOC content and the hypotoxic characteristics of releaser.Under the condition of same coat-thickness, can keep antifouling property more muchly, reduced the maintenance cost of marine antifouling coating.And the VOC content of antifouling paint is low, has reduced air environmental pollution, and what coating discharged is hypotoxic silicone oil, has reduced the pollution to ocean environment.
Of the above embodiment of the present invention, adopt method same or similar and component and other anti-fouling ship paint and the constructional method that obtain, all in protection domain of the present invention with it.
Claims (10)
1. low surface energy anti-fouling ship paint preparation method that can discharge silicone oil is characterized in that it may further comprise the steps:
(1) preparing material: each component and the weight percentage thereof of coating are following:
Fluorine silicon vinyl resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Said powder is for include a kind of in silicon-dioxide, aluminum oxide, the titanium oxide at least;
Said solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, MIBK, MIPK, methyl n-butyl ketone, MIBK, the THF two or more;
Catalyzer is an organotin catalysts.
(2) preparation coating: fluorine silicon vinyl resin, powder, silicone oil, solvent, catalyzer, dispersion agent, the anti-sagging agent of corresponding proportional quantity are carried out dispersing and mixing, make coating.
2. the low surface energy anti-fouling ship paint preparation method that can discharge silicone oil according to claim 1 is characterized in that the preparation method of the fluorine silicon vinyl resin in the described step (1) specifically comprises the steps:
(1.1) preparation first mixing solutions: the weight percentage of first mixing solutions is 5～30%, in YLENE, adds N-BUTYL ACETATE, and uniform mixing makes first mixing solutions; The weight percentage of YLENE in first mixing solutions is 30～70%;
(1.2) preparation second mixing solutions: prepare the raw material of second mixing solutions, each component and the weight percentage thereof of this raw material are following:
TEB 3K 20～50%;
Bing Xisuandingzhi 10～20%;
Rocryl 400 3～10%;
Initiator 0.5～5%;
The mixing solutions 3～20% of fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate,
The mixing solutions of TEB 3K, Bing Xisuandingzhi, Rocryl 400, initiator, fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate of corresponding proportional quantity is carried out uniform mixing make second mixing solutions; The weight percentage of fluorine-containing (methyl) propenoate in the mixing solutions of fluorine-containing (methyl) propenoate and siliceous (methyl) propenoate is 20～80%.
(1.3) drip mixing: first mixing solutions is heated, when being warmed up to 60～100 ℃, slowly be added dropwise to second mixing solutions, until dropwising;
(1.4) insulation: after dropwising, constant temperature kept 2～20 hours, made the fluorine silicon vinyl resin.
3. the low surface energy anti-fouling ship paint preparation method that can discharge silicone oil according to claim 1 is characterized in that,
The median size of the powder in the described step (1) is 20～1000nm;
The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the ZGK 5 that amino ZGK 5, ZGK 5, YSR 3286, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least;
Said dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S;
Said anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
4. the low surface energy anti-fouling ship paint preparation method that can discharge silicone oil according to claim 1 is characterized in that, described step (2), and it specifically comprises the steps:
(2.1) preparation A component: by corresponding proportional quantity fluorine silicon vinyl resin, silicone oil, anti-sagging agent are mixed, and add and have in the whisking appliance of TM, mix down at 35～45 ℃ and stirred 25～35 minutes, make the A component;
More than the quality percentage composition of each component in coating be:
Fluorine silicon vinyl resin 15～50%;
Silicone oil 5～30%;
Anti-sagging agent 0.2～2%,
(2.2) preparation B component: press corresponding proportional quantity with powder, dispersion agent, solvent, catalyst mix, and be transferred in the shredder, start shredder, the speed setting of this shredder is 900～1100 rev/mins, and grinding jitter time is 110～250 minutes;
More than the quality percentage composition of each component in coating be:
Powder 30～20%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
(2.3) A component and B component are mixed, and at room temperature stirred 110～250 minutes, make coating.
5. implement the said coating that can discharge the low surface energy anti-fouling ship paint preparation method preparation of silicone oil of claim 1 for one kind, it is characterized in that its each component and weight percentage thereof are following:
Fluorine silicon vinyl resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Said powder is for include a kind of in silicon-dioxide, aluminum oxide, the titanium oxide at least;
Solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, MIBK, MIPK, methyl n-butyl ketone, MIBK, the THF two or more;
Said catalyzer is an organotin catalysts.
6. coating according to claim 5 is characterized in that, the median size of said powder is 20～1000nm; The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the ZGK 5 that amino ZGK 5, ZGK 5, YSR 3286, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least; Said dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S; Said anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
7. coating according to claim 5 is characterized in that, said flaky material is that sericite or the talcum powder of 1～10 μ m processed by particle size diameter.
8. implement the said execution of coating method of claim 5 for one kind, it is characterized in that it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness handled;
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and this steel anti-corrosion primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 45～80 μ m;
3) the preparation intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 140～210 μ m;
4) coating evenly is coated on the middle layer, forming thickness is the top coat layer of 230～320 μ m.
9. coating according to claim 8 is characterized in that, described steel anti-corrosion primer is a kind of in epoxy zinc rich primer, zinc-rich coating, the thick modified epoxy slurry lacquer, and thickness is 45～80 μ m.
10. coating according to claim 8 is characterized in that, described intermediate coat is epoxy micaceous iron intermediate coat or acrylic polyurethane coating.
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