CN109486314A - A kind of no copper antifouling paint and preparation method thereof - Google Patents
A kind of no copper antifouling paint and preparation method thereof Download PDFInfo
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- CN109486314A CN109486314A CN201811584703.8A CN201811584703A CN109486314A CN 109486314 A CN109486314 A CN 109486314A CN 201811584703 A CN201811584703 A CN 201811584703A CN 109486314 A CN109486314 A CN 109486314A
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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
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
- 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
- C09D5/1625—Non-macromolecular compounds organic
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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
- 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
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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
- 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
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
The present invention provides a kind of no copper antifouling paint and preparation method thereof, wherein, this includes 20-30 parts of main chain degradation-type zinc acrylate resin, 35-46 parts of composite anti-fouling agent, 0.3-1.5 parts of modified manometer silicon dioxide, 6-10 parts of pigments and fillers, 25-30 parts of solvent without copper antifouling paint.Preparation method are as follows: slurries first are made in modified manometer silicon dioxide；It carries out preparing coating using conventional paint preparation process again, in a solvent by the dissolution of main chain degradation-type zinc acrylate resin, modified manometer silicon dioxide slurries, anti-fouling agent, filler and pigment are added under dispersion condition, then by grinding coatings obtained to 50 μm of fineness <.Of the invention high without copper antifouling paint hardness, wear-resisting, impact resistance is excellent, anti-pollution is good；Using can degradable resin and environment-friendly type anti-fouling agent, meet environmental requirements, have a good application prospect.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of no copper antifouling paint and preparation method thereof.
Background technique
The damage that marine biofouling refers to the attachment due to marine organisms, invades and cause underwater facility.Marine organisms
Many adverse effects can be brought to ocean development by being stained, and coating antifouling paint is the main method for solving the problems, such as marime fouling.It is existing
Stage is most widely used with the cupric antifouling paint that cuprous oxide is main anti-fouling agent, and still, cupric anti-fouling paint is to aluminium alloy base
Material has corrosiveness；Moreover, copper ion accumulates in the seawater is unfavorable for marine environment, some countries in Northern Europe have limited oxidation
The cuprous use in antifouling paint.
In addition, the integrality of nonpolluting coating is the basis of guarantee anti-pollution, however, in actual application, it is antifouling
Coating often because hardness or toughness are inadequate, leads to coating damage, antifouling failure.For example, during ship dock repair or navigation
Can because caused by colliding, scratch etc. nonpolluting coating it is damaged, breakage adheres to fouling organism, increases hull ship resistance；For another example, some
The nonpolluting coating on underwater kit surface is prone to wear in hoisting process, and fray adheres to fouling organism, and then causes to fill under water
Standby system down is disturbed.Patent CN107286794A discloses a kind of drag reduction antifouling paint of not cupric class anti-fouling paint
And preparation method thereof, which has good anti-pollution, but to the hardness and toughness for not referring to anti-fouling paint.Patent
CN106883758A discloses a kind of environmentally friendly fishing net without copper antifouling paint, does not also pay close attention to the hardness and toughness of paint film.
In order to avoid nonpolluting coating is during use by the damage of external force, the integrality and antifouling effect of paint film are influenced
Fruit can be improved the toughness and hardness of stain-proofing layer by modified antifouling paint, however rarely record in the prior art it is how right
Antifouling paint is modified to improve its toughness and hardness.
For example, as it is known that nano-material modified coating, can make coating performance get a promotion, be answered in antifouling paint
With.Patent CN106519978A discloses a kind of environment-friendly type marine antifouling coating, is added to 1-3% nano silica, but only
As simple additive, nano silica is not modified, does not also refer to that nano silica rises in the coating
Effect.
High hardness high toughness environmental protection type anti-pollution paint is still relatively deficient in existing market, limits the hair of ocean development industry
Exhibition.
Summary of the invention
In order to solve background technique, to mention high hardness high toughness environmental protection type anti-pollution paint in existing market still relatively deficient
Problem, the present invention provide a kind of no copper antifouling paint, include: in parts by weight
Further, Zn-ef ficiency content is 0.5-20%, preferably 3- in the main chain degradation-type polyacrylic acid zinc resin
10%, acid value 30-300mgKOH/g, preferably 50-230mgKOH/g.
Further, the composite anti-fouling agent includes main anti-fouling agent and auxiliary anti-fouling agent；The main anti-fouling agent includes U.S. support
At least one of miaow pyridine and 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl-pyrroles and zinc pyrithione and 4,
At least one of 5- dichloro dioctyl isothiazoline -3- ketone is combined；The auxiliary anti-fouling agent is the oxygen of 5-30 μm of partial size
Change zinc.
Further, the modified manometer silicon dioxide is by coupling agent modified；The modified manometer silicon dioxide uses
Partial size is the silica of 10-100nm；The coupling agent is 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 3- amino
Propyl trimethoxy silicane, 3- (methylacryloyl) propyl trimethoxy silicane, three ethoxy of 3- (the third oxygen of 2,3- epoxy) propyl
One of base silane, 3-aminopropyltriethoxysilane, 3- (methylacryloyl) propyl-triethoxysilicane are a variety of.
Further, partial size≤30 μm of the pigments and fillers；The pigments and fillers are mainly made of filler and pigment；It is described to fill out
The Mohs' hardness of material is greater than 3；The filler is at least one of titanium dioxide, barium sulfate, quartz sand；The pigment be carbon black,
At least one of toluidine red, phthalocyanine blue, dark green.
Further, the solvent is at least one of dimethylbenzene and propylene glycol methyl ether acetate (PMA).
The present invention also provides a kind of preparation methods of no copper antifouling paint, include the following steps:
S1, partial solvent is taken, modified manometer silicon dioxide is added in solvent, ultrasonic disperse obtains modified Nano two
Silica slurry, it is spare；
S2, main chain degradation-type zinc acrylate resin is dissolved in partial solvent, under dispersion condition, is added made from S1
Nano silica slurries and composite anti-fouling agent and pigments and fillers obtain coating, then by grinding coatings to 50 μm of fineness <.
Further, in S1 step modified manometer silicon dioxide the preparation method comprises the following steps: by nano silica it is dry after plus
Enter ultrasonic disperse in ethanol water, coupling agent/deionized water/dehydrated alcohol hydrolyzate is added, is heated back at 70-80 DEG C
Stream reaction 4-6h, then be centrifuged, clean, it is dried to obtain modified manometer silicon dioxide.
Further, modified manometer silicon dioxide ultrasonic disperse 20-30min in a solvent in S1 step.
Further, the dispersion condition that dispersion condition is revolving speed 2000-2500r/min in S2 step；It is ground in S2 step
Using sand milling or ball milling.
Compared with prior art, no copper antifouling paint provided by the invention passes through main chain degradation zinc acrylate resin, environmental protection
The collocation of composite anti-fouling agent, modified manometer silicon dioxide and high rigidity filler reaches synergistic effect, improves nonpolluting coating
Hardness and toughness, while there is good anti-pollution.Its principle is to utilize high rigidity filler and modified manometer silicon dioxide material
The hardness of itself is expected to promote coating hardness, moreover, modified manometer silicon dioxide is evenly dispersed in the coating, organic group and nothing
Coupling reaction occurs for the other components in copper antifouling paint formula, so that coating system is formed a degree of network structure, favorably
In the hardness and impact resistance that improve coating.In addition, main chain degradation zinc acrylate resin compares common side-chain hydrolysis type third
Olefin(e) acid zinc resin has excellent main chain degradation property, and coating surface can be degraded into nontoxic small point under the action of seawater
Son breaks the network structure of surface covering, is conducive to the release of anti-fouling agent.Therefore, it can not only be improved using the formula system
The hardness and toughness of coating, and can guarantee the anti-pollution of coating in the seawater.
Detailed description of the invention
Fig. 1 is to coat embodiment 1 to illustrate without 1 year sea organism attachment situation of template shallow sea board experiment of copper antifouling paint
Figure.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
It should be noted that in the examples where no specific technique or condition is specified, it is described according to the literature in the art
Technology or conditions or carried out according to product description, reagents or instruments used without specified manufacturer, be that can lead to
Cross the conventional products of commercially available acquisition.
The present invention provides embodiment 1-4 to the present invention will be described.
Embodiment 1
Without copper antifouling paint formula (component is in parts by weight): 20 parts of resin of main chain degradable polypropylene acid zinc；It is compound anti-
40 parts of dirty agent, wherein 6 parts of zinc pyrithione, 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl -9 parts of pyrroles, oxidation
25 parts of zinc；0.5 part of modified manometer silicon dioxide；6 parts of pigments and fillers, wherein 4.5 parts of barium sulfate, 0.5 part of phthalocyanine blue, 1 part of carbon black；
25 parts of solvent, wherein 10 parts of PMA, 15 parts of dimethylbenzene.
Preparation method:
(1), 0.5 part of modified manometer silicon dioxide is added in 2 parts of dimethylbenzene, is placed in ultrasonic disperse in ultrasonic dispersers
Modified manometer silicon dioxide slurries are made in 30min.
(2), 20 parts of resin of main chain degradable polypropylene acid zinc are dissolved in the mixed solvent of 13 parts of dimethylbenzene and 5 parts of PMA
In, it is placed in dispersion machine, revolving speed is controlled in 2000-2500r/min, under this dispersion condition, toward main chain degradable polypropylene acid
Modified manometer silicon dioxide slurries obtained above and 6 parts of zinc pyrithione, 2- (p- chlorobenzene are added in zinc resin lysate
Base) -3- cyano-bromo -5- trifluoromethyl -9 parts of pyrroles, 25 parts of zinc oxide, 4.5 parts of barium sulfate, 0.5 part of phthalocyanine blue, carbon black 1
Part, 1h is reacted, obtains coating, then coating is placed in sand mill and is sanded to fineness less than 50 μm.
Embodiment 2
Without copper antifouling paint formula (component is in parts by weight): 30 parts of resin of main chain degradable polypropylene acid zinc；It is compound anti-
46 parts of dirty agent, wherein 8 parts of zinc pyrithione, 8 parts of dexmedetomidine, 30 parts of zinc oxide；0.3 part of modified manometer silicon dioxide；Face is filled out
10 parts of material, wherein 2 parts of barium sulfate, 3 parts of quartz sand, 5 parts of toluidine red, 1 part of carbon black；30 parts of solvent, wherein 30 parts of dimethylbenzene.
Preparation method:
(1), 0.3 part of modified manometer silicon dioxide is added in 1.2 parts of dimethylbenzene, is placed in ultrasonic disperse in ultrasonic dispersers
Modified manometer silicon dioxide slurries are made in 30min.
(2), by main chain degradable polypropylene acid zinc 30 parts of resin be dissolved in 28.8 parts of xylene solvents, be placed in dispersion machine
In, revolving speed is controlled in 2000-2500r/min, under this dispersion condition, is added toward main chain degradable polypropylene acid zinc resin lysate
Enter modified manometer silicon dioxide slurries obtained above and 8 parts of zinc pyrithione, 8 parts of dexmedetomidine, 30 parts of zinc oxide, sulfuric acid
2 parts of barium, 3 parts of quartz sand, 5 parts of toluidine red, 1 part of carbon black react 1.5h, obtain coating, then coating is placed in ball in ball mill
Fineness is milled to less than 50 μm.
Embodiment 3
Without copper antifouling paint formula (component is in parts by weight): 25 parts of resin of main chain degradable polypropylene acid zinc；It is compound anti-
35 parts of dirty agent, wherein 4,5- 10 parts of ketone of dichloro dioctyl isothiazoline -3-, 2- (p- chlorphenyl) -3- cyano-bromo -5- three
5 parts of methyl fluoride-pyrroles, 20 parts of zinc oxide；1 part of modified manometer silicon dioxide；9.5 parts of pigments and fillers, wherein 4 parts of titanium dioxide, quartz
1 part of sand, 4 parts of dark green, 0.5 part of carbon black；30 parts of solvent, wherein 15 parts of PMA, 15 parts of dimethylbenzene.
Preparation method:
(1), 1 part of modified manometer silicon dioxide is added in 4 parts of dimethylbenzene, is placed in ultrasonic disperse in ultrasonic dispersers
Modified manometer silicon dioxide slurries are made in 30min.
(2), 25 parts of resin of main chain degradable polypropylene acid zinc are dissolved in the mixed solvent of 11 parts of dimethylbenzene and 15 parts of PMA
In, it is placed in dispersion machine, revolving speed is controlled in 2000-2500r/min, under this dispersion condition, toward main chain degradable polypropylene acid
Modified manometer silicon dioxide slurries obtained above and 4,5- dichloro dioctyl isothiazoline -3- ketone is added in zinc resin lysate
10 parts, 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl -5 parts of pyrroles, 20 parts of zinc oxide, 4 parts of titanium dioxide, quartz
1 part of sand, 4 parts of dark green, 0.5 part of carbon black react 2h, obtain coating, then coating is placed in ball mill and is milled to fineness and is less than
50μm。
Embodiment 4
Without copper antifouling paint formula (component is in parts by weight): 20 parts of resin of main chain degradable polypropylene acid zinc；It is compound anti-
40 parts of dirty agent, wherein 4,5- 10 parts of ketone, 10 parts of dexmedetomidine, 20 parts of zinc oxide of dichloro dioctyl isothiazoline -3-；Modification is received
.5 parts of silica 1 of rice；6 parts of pigments and fillers, wherein 5 parts of titanium dioxide, 1 part of carbon black；25 parts of solvent, wherein 15 parts of PMA, diformazan
10 parts of benzene.
Preparation method:
(1), 1.5 parts of modified manometer silicon dioxides are added in 6 parts of dimethylbenzene, are placed in ultrasonic disperse in ultrasonic dispersers
Modified manometer silicon dioxide slurries are made in 30min.
(2), 20 parts of resin of main chain degradable polypropylene acid zinc are dissolved in the mixed solvent of 4 parts of dimethylbenzene and 15 parts of PMA
In, it is placed in dispersion machine, revolving speed is controlled in 2000-2500r/min, under this dispersion condition, toward main chain degradable polypropylene acid
Modified manometer silicon dioxide slurries obtained above and 4,5- dichloro dioctyl isothiazoline -3- ketone is added in zinc resin lysate
10 parts, 10 parts of dexmedetomidine, 20 parts of zinc oxide, 5 parts of modified titanium, 1 part of carbon black react 1h, obtain coating, then coating is set
It is sanded to fineness in sand mill less than 50 μm.
Main chain degradation-type zinc acrylate resin, composite anti-fouling agent, pigments and fillers and solvent used in above-described embodiment 1-4 are equal
For technical grade；Modified manometer silicon dioxide is self-control, preparation method are as follows: water-soluble by ethyl alcohol is added after nano silica drying
3-aminopropyltriethoxysilane coupling agent/deionized water/dehydrated alcohol hydrolyzate is added, in 70- in ultrasonic disperse in liquid
Heating reflux reaction 4-6h at 80 DEG C, then be centrifuged, clean, it is dried to obtain modified manometer silicon dioxide.
The present invention also provides following comparative example 1-3 to compare,
Comparative example 1:
Antifouling paint formula (component is in parts by weight): 20 parts of resin of main chain degradable polypropylene acid zinc；Composite anti-fouling agent
40 parts, wherein 6 parts of zinc pyrithione, 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl -9 parts of pyrroles, zinc oxide 25
Part；5.5 parts of pigments and fillers, wherein 4.5 parts of barium sulfate, 0.5 part of phthalocyanine blue, 1 part of carbon black；20 parts of solvent, wherein 5 parts of PMA, two
15 parts of toluene.
Preparation method:
20 parts of resin of main chain degradable polypropylene acid zinc are dissolved in the in the mixed solvent of 15 parts of dimethylbenzene and 5 parts of PMA, set
In dispersion machine, revolving speed is controlled in 2000-2500r/min, under this dispersion condition, toward main chain degradable polypropylene acid zinc resin
6 parts of zinc pyrithione, 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl -9 parts of pyrroles, zinc oxide 25 is added in lysate
Part, 4.5 parts of barium sulfate, 0.5 part of phthalocyanine blue, 1 part of carbon black react 1.5h, obtain coating, then coating is placed in sand mill and is sanded
To fineness less than 50 μm.
Comparative example 2:
Antifouling paint formula (component is in parts by weight): 20 parts of resin of main chain degradable polypropylene acid zinc；Composite anti-fouling agent
40 parts, wherein 6 parts of zinc pyrithione, 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl -9 parts of pyrroles, zinc oxide 25
Part；5.5 parts of pigments and fillers, wherein 4.5 parts of talcum powder, 0.5 part of phthalocyanine blue, 1 part of carbon black；20 parts of solvent, wherein 5 parts of PMA, two
15 parts of toluene.
Preparation method:
20 parts of resin of main chain degradable polypropylene acid zinc are dissolved in the in the mixed solvent of 15 parts of dimethylbenzene and 5 parts of PMA, set
In dispersion machine, revolving speed is controlled in 2000-2500r/min, under this dispersion condition, toward main chain degradable polypropylene acid zinc resin
6 parts of zinc pyrithione, 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl -9 parts of pyrroles, zinc oxide 25 is added in lysate
Part, 4.5 parts of talcum powder, 0.5 part of phthalocyanine blue, 1 part of carbon black react 2h, obtain coating, then coating is placed in sand mill be sanded to
Fineness is less than 50 μm.
Comparative example 3:
Using commercially available no copper zinc acrylate resin self-polishing coating as antifouling paint.
It should be noted that the component in each embodiment provided by the invention, comparative example is all made of same company, same system
The product of column.
According to GB/T 6739-2006 and GB/T 1732-1993 to embodiment 1, embodiment 2, embodiment 3, embodiment 4,
Comparative example 1, comparative example 2 and comparative example 3 carry out hardness and impact resistance test, and test result is as shown in table 1:
The hardness and impact resistance of 1 nonpolluting coating of table compare
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hardness | 3H | 3H | 2H | 2H | HB | B | HB |
| Impact resistance, cm | 95 | 90 | 100 | 100 | 30 | 45 | 40 |
According to table 1, embodiment 1-4 is obtained without copper antifouling paint, and coating carries out pencil hardness and impact resistance
It can test, hardness reaches 2H or more, and impact resistance reaches 90cm or more, hence it is evident that is better than comparative example 1-3, to demonstrate offer of the present invention
Have the characteristics that hardness is high, toughness is big without copper antifouling paint.
In addition, the present invention has also carried out antifouling test without copper antifouling paint to embodiment 1-4, embodiment 1-4's is antifouling
Coating is coated on aluminum alloy base material, and carries out shallow sea board experiment by GB/T5370-2007, and the test period is a marine growth
Busy season.Wherein, antifouling paint is 60 μ using (roller coating and airless spraying can also be used) construction, per pass thickness of dry film is brushed
M, 3 dry film of coating.Test result is that the antifouling scoring of embodiment 1-4 is all greater than 85 points, and the specimen surface in embodiment 1 is as schemed
Shown in 1, do not occur marine organisms attachment.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of no copper antifouling paint, which is characterized in that include: in parts by weight
2. no copper antifouling paint according to claim 1, which is characterized in that the main chain degradation-type polyacrylic acid zinc resin
Middle Zn-ef ficiency content is 0.5-20%, acid value 30-300mgKOH/g.
3. no copper antifouling paint according to claim 1, which is characterized in that the composite anti-fouling agent include main anti-fouling agent and
Assist anti-fouling agent；The main anti-fouling agent includes dexmedetomidine and 2- (p- chlorphenyl) -3- cyano-bromo -5- trifluoromethyl-pyrrole
It at least one of coughs up and zinc pyrithione and 4, at least one of 5- dichloro dioctyl isothiazoline -3- ketone is combined；
The auxiliary anti-fouling agent is the zinc oxide of 5-30 μm of partial size.
4. no copper antifouling paint according to claim 1, which is characterized in that the modified manometer silicon dioxide is by coupling
Agent is modified；The modified manometer silicon dioxide uses partial size for the silica of 10-100nm；The coupling agent is 3- (2,3- ring
The third oxygen of oxygen) propyl trimethoxy silicane, 3- TSL 8330,3- (methylacryloyl) propyl trimethoxy silicon
Alkane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3-aminopropyltriethoxysilane, 3- (methylacryloyl) third
One of ethyl triethoxy silicane alkane is a variety of.
5. no copper antifouling paint according to claim 1, which is characterized in that partial size≤30 μm of the pigments and fillers；It is described
Pigments and fillers are mainly made of filler and pigment；The Mohs' hardness of the filler is greater than 3；The filler is titanium dioxide, barium sulfate, stone
At least one of sand；The pigment is at least one of carbon black, toluidine red, phthalocyanine blue, dark green.
6. no copper antifouling paint according to claim 1, which is characterized in that the solvent is dimethylbenzene and propylene glycol monomethyl ether
At least one of acetate.
7. a kind of preparation method of no copper antifouling paint, which comprises the steps of:
S1, partial solvent is taken, modified manometer silicon dioxide is added in solvent, ultrasonic disperse obtains modified nano-silica
Silicon slurries, it is spare；
S2, main chain degradation-type zinc acrylate resin is dissolved in partial solvent, under dispersion condition, nanometer made from S1 is added
Silica slurry and composite anti-fouling agent and pigments and fillers obtain coating, then by grinding coatings to 50 μm of fineness <.
8. the preparation method of no copper antifouling paint according to claim 7, which is characterized in that modified Nano two in S1 step
Silica the preparation method comprises the following steps: will nano silica it is dry after ultrasonic disperse in ethanol water is added, coupling agent/go is added
Ionized water/dehydrated alcohol hydrolyzate, the heating reflux reaction 4-6h at 70-80 DEG C, then be centrifuged, clean, it is dried to obtain modification
Nano silica.
9. the preparation method of no copper antifouling paint according to claim 7, which is characterized in that modified Nano two in S1 step
Silica ultrasonic disperse 20-30min in a solvent.
10. the preparation method of no copper antifouling paint according to claim 7, which is characterized in that dispersion condition in S2 step
For the dispersion condition of revolving speed 2000-2500r/min；Grinding is using sand milling or ball milling in S2 step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811584703.8A CN109486314A (en) | 2018-12-24 | 2018-12-24 | A kind of no copper antifouling paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811584703.8A CN109486314A (en) | 2018-12-24 | 2018-12-24 | A kind of no copper antifouling paint and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114836106A (en) * | 2022-06-06 | 2022-08-02 | 季华实验室 | Antifouling paint and preparation method thereof |
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Application publication date: 20190319 |