CN104403448A - Nano cuprous oxide and nano silver compounded sea anti-fouling paint - Google Patents
Nano cuprous oxide and nano silver compounded sea anti-fouling paint Download PDFInfo
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- CN104403448A CN104403448A CN201410570415.2A CN201410570415A CN104403448A CN 104403448 A CN104403448 A CN 104403448A CN 201410570415 A CN201410570415 A CN 201410570415A CN 104403448 A CN104403448 A CN 104403448A
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- cuprous oxide
- nano
- nano silver
- antifouling coating
- oxide composite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a nano cuprous oxide and nano silver compounded sea anti-fouling paint, the cuprous oxide is nanometer or sub nanometer scale, nano silver is synthesized by a chemical method, silver particle content is 6000ppm-24000ppm, the sea anti-fouling paint comprises the following raw materials by mass: 30%-50% of a drag reduction polymer, 20%-25% of toxic materials, 2%-5% of auxiliary materials, 0.1%-0.2% of an efficient anti-fouling agent, 5%-25% of a functional pigment, 10%-20% of a solvent, 1%-1.5% of a plasticizer, and 1%-1.5% of a thixotropic agent, the sea anti-fouling paint has a good performance for matching with an antirusting paint, is smooth and flat in coating film, good in drag reduction performance, uniform in erosion rate, energy saving and consumption reducing, and the sea anti-fouling paint is in medical micro toxic level, cause no harm to the sea environment, and can meet the requirements of environmental protection.
Description
Technical field
The present invention relates to coating, particularly relate to the marine antifouling coating of boats and ships with a kind of nano cuprous oxide composite nano silver.
Background technology
When boats and ships and some underwater units run in ocean, there are many biologies can be attached to hull bottom and ocean underwater facility in ocean, these settled organismes endanger huge to boats and ships and ocean underwater facility, they significantly increase hull mass (on average up to 20kg/m2), increase running resistance, affect ship's speed, thus increase fuel consumption.It is reported, hull bottom surface often increases by 10 μm of roughness, and fuel consumption will increase by 1%, and settled organism can accelerate marine corrosion, increases frequency of maintenance of marching into the arena; Settled organism also brings maritime facilitieies such as marine drilling platform, seawater pipeline, sonar domes and has a strong impact on.In the method preventing sea marine organism pollution, antifouling paint is used to be the most extensive and effective means.
Antifouling paint adopts the compound such as mercury, arsenic for poison material in early days.It is that poison is expected that the 1950's occurs with Red copper oxide, and rosin, ethenoid resin and chlorinated rubber are the antifouling varnish of base-material; The sixties, organo-tin compound was applied in antifouling varnish.Organo-tin compound both can be used alone, also can with Red copper oxide with the use of, because it has broad-spectrum sterilization, antifouling phase effect is improved significantly; Arrive the mid-1970s, rise containing organotin self polishing copolymer antifouling paint (SPC), vinylformic acid organotin polymer is base-material, is again stain control agent, is slowly hydrolyzed under the effect of seawater, discharge organotin groups, remaining organotin polymer has necessarily water-soluble and swelling property simultaneously, forms smooth surface, landing resistance effect, such continuous renewal surface, continuous uniform discharges toxic agent and plays long-acting and anti-fouling effect; On the other hand, according to relevant research, organo-tin compound has strong toxicity and not easily degrades.Organotin content is higher than 0.1 × 10
-6seawater will affect the marine eco-environment, has a strong impact on marine growth breeding, even causes heritable variation.Because organotin content in SPC is up to 30% ~ 50%, the problem that ocean pollutes is become increasingly conspicuous.Therefore, research and develop Tin-free Spc Anti-fouling Paint of new generation (TP-SPC), no matter be all of great practical significance economically or militarily.It is reported, 2012, certain marine laboratory domestic develops sub-nano cuprous oxide marine antifouling coating project with certain institution cooperation Japanese, but Red copper oxide addition is larger, need to add more than 40% to and just have obvious anti-fouling effect, cause the water tolerance of coating, the large spoke of snappiness reduces, and Red copper oxide belongs to micro-malicious level, when addition is large, though little on the impact of ocean environment, but also can cause certain destruction, research and develop a kind of antifouling paint of composite nano Red copper oxide, have efficient, long-acting, the important meaning of environmental protection, this project is under this technical background, a kind of compound nano cuprous oxide composite nano silver antifouling paint is proposed, anti fouling poisonous agent can reduce by 50% consumption, nanometer silver is chemical process preparation, and be aqueous sol, nontoxic, add convenient and safe stable, final film is smooth, excellent physical properties, anti-fouling effect is remarkable.
Summary of the invention
Main purpose of the present invention is the marine antifouling coating providing a kind of nano cuprous oxide composite nano silver, this coating and rust proof paint matching performance good, film is smooth, resistance-reducing performance is good, erosive rate is even, and energy-saving and cost-reducing, this coating belongs to the micro-malicious level of medical science simultaneously, do not endanger ocean environment, meet environmental requirement.
The invention provides a kind of marine antifouling coating of nano cuprous oxide composite nano silver, comprise the raw material of following mass percent:
Preferably, described in fall resistance superpolymer as the base-material of the marine antifouling coating of nano cuprous oxide composite nano silver, elect polyacrylic resin as.
Preferably, poison material elects nano cuprous oxide or Subnano-class cuprous oxide powder as.
Preferably, auxiliary base-material elects chlorinated rubber or Gum Rosin as.
Preferably, nano silver colloidal sol is elected in high-efficiency pollution-proof agent as, and its production stage is as follows:
Preparation solution A: Silver Nitrate, ammoniacal liquor and distilled water are mixed with silver ammino solution, and the pH value of silver ammino solution is between 10 ~ 11;
Preparation B solution: poly-methyl pyrrole alkane ketone is mixed with maltose, and adds carboxylate polymer's dispersion agent and distilled water;
Solution A and B solution are slowly mixed, and regulates pH about 8 with ammoniacal liquor; The obtained nano silver colloidal sol when ultrasonic insulation, adds the concentration that distilled water regulates silver ions in nano silver colloidal sol.
Preferably, functional pigment elects one or more in zinc oxide, talcum powder, iron oxide red or natural capsicum element as.
Preferably, the mixing solutions of one or more in No. 200 coal tar solvents, dimethylbenzene, pimelinketone elected as by solvent.
Preferably, softening agent elects fluorochemical surfactant or wax slurry as.
Preferably, wilkinite elected as by thixotropic agent.
The invention has the beneficial effects as follows: have long-acting and anti-fouling and fall the energy-conservation feature of resistance, meet environmental protection requirement simultaneously, real extra large toxicant leaching rate controls reasonably stability, supporting good with rust proof paint, good physical properties; Film is smooth, and resistance-reducing performance is good, and erosive rate is even, energy-saving and cost-reducing; Belong to the micro-malicious level of medical science, do not endanger ocean environment, meet environmental requirement.
Embodiment
Hereafter will describe the marine antifouling coating of nano cuprous oxide composite nano silver provided by the present invention in conjunction with specific embodiments in detail.It should be noted that the combination of technical characteristic or the technical characteristic described in following embodiment should not be considered to isolated, they mutually can be combined and be combined with each other thus reach better technique effect.
The raw material that the marine antifouling coating of nano cuprous oxide composite nano silver of the present invention comprises and mass percent are: fall resistance superpolymer 30-50%, poison material 20-25%, auxiliary base-material 2-5%, high-efficiency pollution-proof agent 0.1-0.2%, functional pigment 5-25%, solvent 10-20%, softening agent 1-1.5%, thixotropic agent 1-1.5%
The preparation of sodium rice silver sol:
Preparation solution A: the Silver Nitrate of 1.20g ~ 4.8g and appropriate ammoniacal liquor and distilled water are mixed with silver ammino solution 30g, and the pH value of silver ammino solution is between 10 ~ 11;
Preparation B solution: 0.736g ~ 0.864g polyvinylpyrrolidone is mixed with 3.01g maltose, and adds 0.33g carboxylate polymer dispersion agent and distilled water, obtain solution 30g, wherein barley-sugar and Ag
+mol ratio can between 1.2 ~ 1.5;
A and B is slowly mixed, and regulates pH about 8 with ammoniacal liquor; The obtained nano silver colloidal sol when ultrasonic 0.5 ~ 1.5h, 50 ~ 70 degrees Celsius of insulation 10h, stirs and adds distilled water and can obtain the nano silver colloidal sol of silver particles content between 6000 ~ 24000ppm.Regulate pH about 7, stir, keep in Dark Place.Whole preparation process keeps the cleaning of instrument and reagent, and old packaging container must not contain halogens.
Embodiment 1
A marine antifouling coating for nano cuprous oxide composite nano silver, its formula and mass percent are: acrylic resin 40%, chlorinated rubber 4%, nano cuprous oxide 20%, nano silver colloidal sol 0.1%, talcum powder 5%, zinc oxide 8%, iron oxide red 10%, wax slurry 1%, wilkinite 1%, natural capsicum element 1%, mixed solvent 13%.
Embodiment 2
A marine antifouling coating for nano cuprous oxide composite nano silver, its formula and mass percent are: acrylic resin 40%, chlorinated rubber 4%, nano cuprous oxide 25%, nano silver colloidal sol 0.2%, talcum powder 5%, zinc oxide 8%, iron oxide red 10%, wax slurry 1%, wilkinite 1%, mixed solvent 13%.
Embodiment 3
A marine antifouling coating for nano cuprous oxide composite nano silver, its formula and mass percent are: acrylic resin 40%, chlorinated rubber 4%, nano cuprous oxide 20%, nano silver colloidal sol 0.2%, talcum powder 5%, zinc oxide 8%, iron oxide red 10%, wax slurry 1%, wilkinite 1%, mixed solvent 13%.
Based on the marine antifouling coating of a kind of nano cuprous oxide composite nano silver of above-mentioned formula, when testing, the process of test surface of steel plate, to Sa2.5 level, is coated with the epoxide coal bituminous rust proof paint of 4 road 2#, be coated with 4 road antifouling paints of the present invention again, then carry out the detection of real sea water envrionment test.
Traditional performance detects:
Table 1: coating property detected result
Erosive rate measures: on tinplate cylinder, apply the epoxide coal bituminous rust proof paint of 2#, spray 2 road antifouling paints of the present invention again, total coating thickness about 300 μm, tinplate cylinder is installed on homogenizer, and be dipped in the tank containing natural sea-water, at room temperature rotate with 15 pitch line velocities, every day 6-7h, then leave standstill 17-18h.Test period is 1 year.
Toxotest: sample is ground to 200 orders, is made into suspension with rapeseed oil.Laboratory animal is healthy Kunming mouse, male and female half and half, carries out per os contamination and Skin contamination test respectively.According to the acute grade scale of industrial poison, per os of the present invention and all belong to micro-malicious level through skin.
Marine applications is tested: apply antifouling paint of the present invention on the test ship of two batches after, and under test ship, water normally works, and checks after 3 years, wherein a BT(batch testing) ship film is without sea organism attachment, film coated surface is smooth, and color, as newly, obtains 3 years antifouling phase effects; On another BT(batch testing) ship, sea organism attachment area only accounts for 5% of test area, rest part without marine life, smooth surface.
Although give some embodiments of the present invention, it will be understood by those of skill in the art that without departing from the spirit of the invention herein, can change embodiment herein.Above-described embodiment is exemplary, should using embodiment herein as the restriction of interest field of the present invention.
Claims (10)
1. a marine antifouling coating for nano cuprous oxide composite nano silver, is characterized in that, comprises the raw material of following mass percent:
2. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described in fall resistance superpolymer as base-material, be polyacrylic resin.
3. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described poison material is nano cuprous oxide powder or sub-nano cuprous oxide powder.
4. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described auxiliary base-material is chlorinated rubber or Gum Rosin.
5. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described high-efficiency pollution-proof agent is nano silver colloidal sol.
6. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described functional pigment is one or more in zinc oxide, talcum powder, iron oxide red or natural capsicum element.
7. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described solvent is the mixing solutions of one or more in No. 200 coal tar solvents, dimethylbenzene, pimelinketone.
8. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described softening agent is fluorochemical surfactant or wax slurry.
9. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 1, is characterized in that: described thixotropic agent is wilkinite.
10. the marine antifouling coating of nano cuprous oxide composite nano silver according to claim 5, is characterized in that: the preparation method of described nano silver colloidal sol comprises the following steps:
Preparation solution A: Silver Nitrate, ammoniacal liquor and distilled water are mixed with silver ammino solution, and the pH value of silver ammino solution is between 10 ~ 11;
Preparation B solution: poly-methyl pyrrole alkane ketone is mixed with maltose, and adds carboxylate polymer's dispersion agent and distilled water;
Solution A and B solution are slowly mixed, and regulates with ammoniacal liquor
ph is about 8; The obtained nano silver colloidal sol when ultrasonic insulation, adds the concentration that distilled water regulates silver ions in nano silver colloidal sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410570415.2A CN104403448A (en) | 2014-10-23 | 2014-10-23 | Nano cuprous oxide and nano silver compounded sea anti-fouling paint |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410570415.2A CN104403448A (en) | 2014-10-23 | 2014-10-23 | Nano cuprous oxide and nano silver compounded sea anti-fouling paint |
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| CN104403448A true CN104403448A (en) | 2015-03-11 |
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| CN201410570415.2A Pending CN104403448A (en) | 2014-10-23 | 2014-10-23 | Nano cuprous oxide and nano silver compounded sea anti-fouling paint |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106939254A (en) * | 2017-03-07 | 2017-07-11 | 瑞娃科技（重庆）有限公司 | A kind of water cleans nano-resin and preparation method thereof |
| CN106947391A (en) * | 2017-03-21 | 2017-07-14 | 东莞市基核材有限公司 | A kind of antifouling paint and its application in nuclear power station refrigerated sea water circulating line is antifouling |
| CN109021747A (en) * | 2018-07-02 | 2018-12-18 | 巢湖市天宇渔具有限公司 | A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion |
| CN114891439A (en) * | 2022-04-29 | 2022-08-12 | 中油新星纳米工程技术有限公司 | Preparation method of low-surface-energy marine antifouling paint |
| CN114891402A (en) * | 2022-04-29 | 2022-08-12 | 中油新星纳米工程技术有限公司 | Preparation method of vanadium and silver nano-optimized low-surface-energy antifouling paint |
| CN116731574A (en) * | 2023-07-05 | 2023-09-12 | 常州市天盾涂料有限公司 | Tin-free self-polishing antifouling paint and preparation method thereof |
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2014
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Patent Citations (5)
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| EP2441809A1 (en) * | 2009-06-08 | 2012-04-18 | Nitto Kasei Co., Ltd. | Antifouling coating composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by forming the coating film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106939254A (en) * | 2017-03-07 | 2017-07-11 | 瑞娃科技（重庆）有限公司 | A kind of water cleans nano-resin and preparation method thereof |
| CN106947391A (en) * | 2017-03-21 | 2017-07-14 | 东莞市基核材有限公司 | A kind of antifouling paint and its application in nuclear power station refrigerated sea water circulating line is antifouling |
| CN109021747A (en) * | 2018-07-02 | 2018-12-18 | 巢湖市天宇渔具有限公司 | A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion |
| CN114891439A (en) * | 2022-04-29 | 2022-08-12 | 中油新星纳米工程技术有限公司 | Preparation method of low-surface-energy marine antifouling paint |
| CN114891402A (en) * | 2022-04-29 | 2022-08-12 | 中油新星纳米工程技术有限公司 | Preparation method of vanadium and silver nano-optimized low-surface-energy antifouling paint |
| CN116731574A (en) * | 2023-07-05 | 2023-09-12 | 常州市天盾涂料有限公司 | Tin-free self-polishing antifouling paint and preparation method thereof |
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