CN108329783B - Marine antifouling paint and preparation method thereof - Google Patents

Marine antifouling paint and preparation method thereof Download PDF

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CN108329783B
CN108329783B CN201810082242.8A CN201810082242A CN108329783B CN 108329783 B CN108329783 B CN 108329783B CN 201810082242 A CN201810082242 A CN 201810082242A CN 108329783 B CN108329783 B CN 108329783B
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antifouling paint
agent
acrylic resin
marine antifouling
capsaicin
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CN108329783A (en
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张雷
冯正
朱立新
李向东
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Nantong Comens New Materials Co ltd
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Nantong Comens New Materials Co ltd
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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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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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    • 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
    • C09D5/1668—Vinyl-type polymers
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    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
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    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • 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
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    • C08K2003/2272—Ferric oxide (Fe2O3)
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles

Abstract

The invention discloses a marine antifouling paint which comprises the following components in percentage by weight: 30-50% of film-forming base material, 1-10% of composite anti-fouling agent, 2-10% of pigment, 1-5% of filler, 15-40% of solvent and 2-5% of auxiliary agent, wherein the composite anti-fouling agent is prepared from the following components in percentage by weight of 1: 3-1: 10, the component A is 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone, the component B is a capsaicin derivative biocide, and the film forming base material is acrylic resin containing capsaicin derivatives. The paint does not contain toxic substances such as tin or copper and the like which have great harm to the environment, takes 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone and a capsaicin derivative as a combined antifouling agent, has small pollution, combines the sterilization effect of resin, has high and durable antifouling effect and low addition of the antifouling agent, is an environment-friendly antifouling paint, and has simple preparation method and reasonable cost.

Description

Marine antifouling paint and preparation method thereof
Technical Field
The invention relates to the technical field of antifouling paint, in particular to a marine antifouling paint and a preparation method thereof.
Background
Marine pollution refers to the process of attaching and accumulating marine polluting organisms on the surface of artificial facilities immersed in the sea bottom. Seriously affecting the marine industry. Especially, marine vessel pollution is serious. Marine fouling organisms are attached to the bottom of a boat, so that the sailing resistance is increased, the boat speed is reduced, the fuel consumption is increased, the pollution discharge is increased, the performance of marine working equipment is reduced due to pollution attached to the marine working equipment, and the like; severely restricting the development of ocean economy. The economic loss due to marine fouling is about $ 15 billion each year around the world. Therefore, marine antifouling is a significant scientific research issue.
The traditionally effective antifouling method is coatings containing TBT biocides, however such coatings also have biocidal effect on non-target organisms, so the international maritime office banned the use of marine antifouling coatings containing TBT since 2008. The polishing type copper oxide or zinc oxide becomes the mainstream of the prior art, and although the polishing type copper oxide or zinc oxide meets the current environmental protection requirement, a large amount of copper and zinc elements are accumulated in the ocean, so that a large amount of marine life is killed, and the ecological balance is damaged. Therefore, environmental friendly antifouling paints have become a hot spot of research. The currently researched environment-friendly antifouling paint mainly comprises a biological enzyme degradation type antifouling paint, a bionic antifouling paint, a nano antifouling paint, a conductive antifouling paint, a low-surface-energy antifouling paint and the like.
However, a marine antifouling paint with high efficiency and low toxicity is still lacked so far. Therefore, the optimization, re-development and adaptive innovation of the various technologies mentioned above, and the research of novel methods and preparation technologies of ship antifouling paints are one of the important research directions in which the development of ship antifouling paints is urgently needed at present.
Disclosure of Invention
In order to solve the problems, the invention provides a marine antifouling paint and a preparation method thereof, overcomes the defects of high preparation cost, great harm to the environment, poor antifouling durability and the like of the existing marine antifouling paint, and provides a novel marine antifouling paint which is environment-friendly and has strong antifouling capacity.
The technical scheme adopted by the invention is as follows: the marine antifouling paint consists of the following components in percentage by weight: 30-50% of film-forming base material, 1-10% of composite anti-fouling agent, 2-10% of pigment, 1-5% of filler, 15-40% of solvent and 2-5% of auxiliary agent, wherein the composite anti-fouling agent is prepared from the following components in percentage by weight of 1: 3-1: 10, the component A is 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone, the component B is a capsaicin derivative biocide, and the film forming base material is acrylic resin containing capsaicin derivatives.
The capsaicin derivative is at least one of eugenol, N- (4-hydroxy-3-methylbenzyl) acrylamide and N- (4-hydroxy-2-methyl-5-methylthiobenzyl) acrylamide.
The pigment is iron oxide red.
The filler is at least one selected from zinc oxide, zeolite, fumed silica, organic bentonite and titanium dioxide.
The solvent is at least one of dimethylbenzene, cyclohexanone, dimethyl phthalate, butyl acetate and n-butanol.
The auxiliary agent is at least one of a dispersing agent and a flatting agent.
The dispersing agent is BYK-P104 (low molecular weight unsaturated polycarboxylic acid polymer solution) or BYK-163 (high molecular weight block copolymer solution containing pigment affinity groups), and the flatting agent is 3033 (polyether modified organic silicon) or BYK-306 (polyether modified polydisiloxane copolymer solution).
Preferably, the marine antifouling paint consists of the following components in percentage by weight: 30-50% of acrylic resin, 2-10% of iron oxide red, 2-5% of fumed silica, 1-10% of a combined antifouling agent, 5-20% of xylene, 10-20% of butyl acetate and 2-5% of an auxiliary agent, wherein the acrylic resin is acrylic resin containing N- (4-hydroxy-2-methyl-5-methylthiobenzyl) acrylamide or acrylic resin containing eugenol capsaicin derivatives.
The general formula of the acrylic resin containing the eugenol capsaicin derivative is as follows:
Figure 100002_DEST_PATH_IMAGE001
wherein R1 and R2 are OH and COCH2OCH3Or OCH2CH3，a=30-70、b=30-100、c=30-70、d=30-80。
The preparation method of the marine antifouling paint comprises the following steps: fully dispersing the filler and the pigment with the formula amount on a high-speed coating dispersion machine for at least 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid mixture into a mixed liquid containing a film-forming base material, a combined antifouling agent, an auxiliary agent and a solvent according to the formula amount, uniformly stirring under the action of high-shear stirring, adding the rest solvent, and adjusting the viscosity to be 60s (Saybolt universal viscosity).
The specific technical principle is as follows: the peppery taste is a strong pungent smell, the contact killing effect of natural peppery essence on pests is obvious, and after the microorganisms eat the peppery essence, detoxification enzyme systems are inhibited, digestion and absorption are influenced, respiratory metabolism is interfered, and normal physiological activities of the microorganisms are hindered to cause pathological changes and death due to incapability of growth and development. The strong pungent odor of capsaicin also has a repelling effect on microorganisms, so that the microorganisms are not easy to approach the coating, thereby reducing the microbial contamination on the surface. Experiments show that 0.063mg/ml of capsaicin has obvious inhibition effect on bacteria, which indicates the high efficiency of the capsaicin, and the capsaicin substances are nontoxic to marine organisms and have obvious avoidance effect on fouling organisms.
The capsaicin-containing polymer resin also has contact biocidal efficacy. Meanwhile, 4-5 dichloro-2-n-octyl-4-isothiazolin-3-ketone modified by adding marine antifouling agent extracted from natural activity in the sea is a widely used nontoxic marine antifouling agent, and the antifouling agent has good inhibition effect on diatom, bacteria, algae, barnacle and other animals and high efficiency. Moreover, the biocide can be decomposed by hydrolysis, photodegradation and biodegradation, does not accumulate and does not pollute the marine environment. Therefore, the biological avoidance of the capsaicin is combined with the anti-fouling effect of the organic biocide, and the biological pollution on the surface of the ship can be efficiently and synergistically reduced.
Therefore, the synergistic effect of the antibacterial coating is as follows: (1) the released capsaicin has an evasive effect on microorganisms, so that the microorganisms are not easy to attach to the surface of a ship body; (2) the 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone natural biocide modified by adding the marine antifouling agent has good inhibition effect on diatom barnacle microorganisms and prevents the diatom barnacle microorganisms from attaching to the surface of a ship body; (3) the coating resin contains the capsaicin biocide, so that the contact biocidal effect can be generated when microorganisms contact the surface of the coating, and the self-polishing effect of the resin is assisted, so that the killed microorganisms can be removed in time, and the surface of the ship body is kept free from pollution.
The invention has the beneficial effects that: 1. the invention does not contain toxic substances such as tin or copper which have great harm to the environment, and the like, and the antifouling paint is prepared by combining the biocide of 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone and the capsaicin derivative with the antifouling agent and improving the antifouling effect and the durability through the synergistic effect of the two.
2. The invention combines the double effects of 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone and the capsaicin derivative biocide, the antifouling effect of the antifouling paint is high-efficiency and durable, the addition amount of the antifouling agent is lower, the preparation method is simple, and the cost is reasonable.
3. The single-component acrylic resin containing the capsaicin derivative adopted by the invention is taken as a film-forming base material, so that the single-component acrylic resin has a certain antifouling effect, and the environment-friendly marine antifouling paint is prepared.
4. The two-component biocide, 4-5 dichloro-2-n-octyl-4-isothiazoline-3-ketone and capsaicin derivative biocide, adopted by the invention has good inhibition effect on animals such as diatom, bacteria, algae, barnacle and the like, has high efficiency, can be quickly decomposed through hydrolysis, photodegradation and biodegradation, does not generate accumulation effect, and is very safe to marine environment.
5. Overcomes the defects of high preparation cost, great harm to the environment, poor antifouling durability and the like of the existing ship antifouling paint, and provides a brand-new environment-friendly marine antifouling paint with strong antifouling capacity.
Drawings
FIG. 1 is a comparison graph of antifouling effect of a real sea hanging plate (a real sea hanging plate, namely hanging plate in sea water) for 62 days (the back surface is not brushed with antifouling paint).
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
DCOIT (4-5 dichloro-2-n-octyl-4-isothiazolin-3-one) selected in the following examples is directly purchased from manufacturers and is used as white powder which is well dispersed in an organic solvent; the selected capsaicin derivative biocide is an organic biocide synthesized by the user; the selected resin is self-synthesized acrylic resin containing capsaicin derivatives and having a sterilization function.
Example 1
Preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 250g of acrylic resin containing eugenol capsaicin derivative, 25g of iron oxide red, 25g of BYK-P104, 10g of fumed silica, 30g of composite antifouling agent, 60g of xylene and 100g of butyl acetate.
The preparation process comprises the following steps: fully dispersing 10g of fumed silica, 25g of iron oxide red and 25g of BYK-P104 on a coating high-speed dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 250g of eugenol capsaicin derivative acrylic resin, 30g of combined antifouling agent (6 g of A component and 24g of B component), 30g of xylene and 50g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), adding 80g of the rest xylene and butyl acetate, and adjusting the viscosity to 60 s.
Example 2
1kg of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 400g of acrylic resin containing eugenol capsaicin derivative, 100g of iron oxide red, 50g of zeolite, 50g of BYK-163, 80g of composite antifouling agent, 170g of n-butyl alcohol and 150g of butyl acetate.
The preparation process comprises the following steps: fully dispersing 50g of zeolite, 100g of iron oxide red and 50g of BYK-163 on a coating high-speed dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 400g of eugenol capsaicin derivative acrylic resin, 80g of combined antifouling agent (8 g of A component and 72g of B component), 100g of n-butyl alcohol and 50g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), simultaneously adding 170g of the rest n-butyl alcohol and butyl acetate, and adjusting the viscosity to 60 s.
Example 3
1kg of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 400g of acrylic resin containing eugenol capsaicin derivative, 50g of iron oxide red, 50g of zinc oxide, 50g of flatting agent 3033, 80g of composite antifouling agent, 170g of n-butyl alcohol and 200g of butyl acetate.
The preparation process comprises the following steps: fully dispersing 50g of zinc oxide, 50g of iron oxide red and 50g of flatting agent 3033 on a coating high-speed dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 400g of eugenol capsaicin derivative acrylic resin, 80g of combined antifouling agent, (20 g of component A, 60g of component B) 60g of n-butyl alcohol and 100g of butyl acetate, and then uniformly stirring the mixture under the action of high shear (1500/min) stirring, simultaneously adding 210g of the rest n-butyl alcohol and butyl acetate, and adjusting the viscosity to 60 s.
Example 4
1kg of single-component acrylic acid capsaicin derivative resin marine antifouling paint is prepared by the following steps: the components in the formula are weighed as follows: 500g of acrylic resin containing N- (4-hydroxy-2-methyl-5-methylthiobenzyl) acrylamide, 100g of iron oxide red, 50g of organic bentonite, 40g of BYK-306, 80g of composite antifouling agent, 130g of xylene and 100g of N-butyl alcohol.
The preparation process comprises the following steps: fully dispersing 50g of organic bentonite, 100g of iron oxide red and 40g of BYK-306 on a coating high-speed dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing N- (4-hydroxy-2-methyl-5-methylthiobenzyl) acrylamide acrylic resin, 80g of combined antifouling agent (15 g of component A and 65g of component B), 100g of xylene and 50g of N-butyl alcohol, and then stirring the mixture uniformly under the action of high shear (1500/min) stirring, and simultaneously adding 80g of the rest N-butyl alcohol and xylene to adjust the viscosity to 60 s.
Example 5:
preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 250g of acrylic resin containing eugenol capsaicin derivative, 20g of iron oxide red, 25g of titanium dioxide, 10g of BYK-306, 30g of composite antifouling agent, 65g of dimethylbenzene and 100g of butyl acetate.
The preparation process comprises the following steps: fully dispersing 10g of BYK-306, 20g of iron oxide red and 25g of titanium dioxide on a high-speed coating dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 250g of eugenol capsaicin derivative acrylic resin, 30g of combined antifouling agent (5 g of A component and 25g of B component), 30g of xylene and 50g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), adding 85g of the rest xylene and butyl acetate, and adjusting the viscosity to 60 s.
Example 6
Preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 150g of acrylic resin containing eugenol capsaicin derivative, 50g of iron oxide red, 25g of titanium dioxide, 25g of BYK-306, 50g of composite antifouling agent, 100g of xylene and 100g of cyclohexanone.
The preparation process comprises the following steps: fully dispersing 25g of BYK-306, 50g of iron oxide red and 25g of titanium dioxide on a high-speed coating dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 150g of eugenol capsaicin derivative acrylic resin, 50g of combined antifouling agent (10 g of component A and 40g of component B), 30g of xylene and 50g of cyclohexanone, stirring the mixture uniformly under the action of high shear (1500/min), adding 120g of the rest xylene and cyclohexanone, and adjusting the viscosity to 60 s.
Example 7
Preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 250g of acrylic resin containing eugenol capsaicin derivative, 10g of iron oxide red, 5g of titanium dioxide, 10g of BYK-306, 25g of composite antifouling agent, 100g of dimethyl phthalate and 100g of butyl acetate.
The preparation process comprises the following steps: fully dispersing 10g of BYK-306, 10g of iron oxide red and 5g of titanium dioxide on a high-speed coating dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 250g of eugenol capsaicin derivative acrylic resin, 25g of combined anti-fouling agent (5 g of A component and 20g of B component), 40g of dimethyl phthalate and 50g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), adding 110g of the rest dimethyl phthalate and butyl acetate, and adjusting the viscosity to 60 s.
Example 8
Preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 250g of acrylic resin containing eugenol capsaicin derivative, 25g of iron oxide red, 15g of titanium dioxide, 20g of BYK-306, 5g of composite antifouling agent, 85g of dimethylbenzene and 100g of butyl acetate.
The preparation process comprises the following steps: sufficiently dispersing 20g of BYK-306, 25g of iron oxide red and 15g of titanium dioxide on a high-speed coating dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 250g of eugenol capsaicin derivative acrylic resin, 5g of combined antifouling agent (0.5 g of A component and 4.5g of B component), 30g of xylene and 50g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), simultaneously adding 105g of the rest xylene and butyl acetate, and adjusting the viscosity to 60 s.
Example 9
Preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 250g of acrylic resin containing eugenol capsaicin derivative, 50g of iron oxide red, 25g of titanium dioxide, 25g of BYK-306, 50g of composite antifouling agent, 50g of dimethylbenzene and 50g of butyl acetate.
The preparation process comprises the following steps: fully dispersing 25g of BYK-306, 50g of iron oxide red and 25g of titanium dioxide on a high-speed coating dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 250g of eugenol capsaicin derivative acrylic resin, 50g of combined antifouling agent (10 g of A component and 40g of B component), 30g of xylene and 30g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), adding 40g of the rest xylene and butyl acetate, and adjusting the viscosity to 60 s.
Example 10
Preparing 500g of single-component acrylic resin marine antifouling paint containing capsaicin derivatives: the components in the formula are weighed as follows: 200g of acrylic resin containing eugenol capsaicin derivative, 25g of iron oxide red, 25g of titanium dioxide, 10g of BYK-306, 40g of composite antifouling agent, 100g of xylene and 100g of butyl acetate.
The preparation process comprises the following steps: sufficiently dispersing BYK-30610 g, 25g of iron oxide red and 25g of titanium dioxide on a coating high-speed dispersion machine (1500/min) for not less than 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid dispersion into a mixed liquid containing 200g of eugenol capsaicin derivative acrylic resin, 40g of combined anti-fouling agent (10 g of A component and 30g of B component), 50g of xylene and 40g of butyl acetate, stirring the mixture uniformly under the action of high shear (1500/min), adding 110g of the rest xylene and butyl acetate, and adjusting the viscosity to 60 s.
The antifouling paint prepared by the embodiment is subjected to an antifouling paint-like shallow sea immersion test by referring to the methods specified in the national standard GB/T5370-2007 and the national standard GB/T5370-2007. The test time was between 9 and 30 months in 2017 and 12 and 1 months in 2017 (two months total), and the results of the shallow sea immersion test are shown in fig. 1 (comparative examples are commercial antifouling paint for rainbow geriatric and PVC panels).
The shallow sea immersion test was carried out using example 1 and the results are shown in table 1:
Figure 545147DEST_PATH_IMAGE002
。
as can be seen from fig. 1, the surface of the coating prepared in example 1 remained clean after soaking for two months, and no contamination or fouling was observed; the surface of the control group is seriously stained and basically covered by the seaweed, which shows that the antifouling performance of the coating of the embodiment is excellent; the surface fouling as a blank control group was severe and was essentially covered by seaweed, indicating that the addition of a coating containing an antifouling agent helps to reduce marine biofouling.
Anti-escherichia coli adhesion test:
the coating resins prepared in examples 1, 2, 3, 4, 5 and the biocide-free acrylic varnishes (comparative examples) were applied in an amount of 10 mg each to 1cm2On the steel sheet, removing all solvent on the oven and vacuum drying oven, to be tested, culturing Escherichia coli to OD 1.0 (at this time, the bacteria growth speed is fastest), diluting 10 times, using it as test bacteria liquid, respectively placing the samples to be tested into 24-hole plates, adding 1ml of test bacteria liquid into each hole, incubating 1.5h (100 rpm, 37 ℃) by shaking table, transferring the samples to be tested into new holes, adding 1ml of sterile PBS into each hole, washing 10min by shaking table at 200rpm, then changing fresh sterile PBS, repeating washing operation, 3 times, removing the Escherichia coli with weak adhesion on the coating surface, after washing, transferring the samples into new holes, adding 1ml of sterile PBS into each hole, performing 50% power ultrasonic 30s, stopping for 30s, repeating for 4 times, completely eluting the Escherichia coli adhered on the coating surface, taking 50 mu L plates from each sample hole, culturing the eluents on solid culture medium at 37 ℃ for 12 h, counting viable bacteria on the plates (colony forming number, CFU), calculating the sample adhesion amount (CFU)2) = (colony formation number (CFU) × 1/0.05)/1 cm2(ii) a The adhesion rate against E.coli was calculated as follows: adhesion rate (%) against escherichia coli = (AE)Varnish-AESample (I)）/AEVarnish。
The results of the test of the adhesion rate of the multifunctional modified antifouling paint resin to escherichia coli are shown in table 2:
Figure DEST_PATH_IMAGE003
。
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. The marine antifouling paint is characterized by comprising the following components in percentage by weight: 30-50% of film-forming base material, 1-10% of composite anti-fouling agent, 2-10% of pigment, 1-5% of filler, 15-40% of solvent and 2-5% of auxiliary agent, wherein the composite anti-fouling agent is prepared from the following components in percentage by weight of 1: 3-1: 10, the component A is 4, 5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, the component B is a capsaicin derivative biocide, and the film-forming base material is acrylic resin containing eugenol capsaicin derivatives, and has the general formula:
Figure DEST_PATH_IMAGE001
in the formula, R1、 R2Is OH, COCH2OCH3Or OCH2CH3，a=30-70、b=30-100、c=30-70、d=30-80。
2. A marine antifouling paint according to claim 1, wherein the capsaicin derivative is at least one selected from N- (4-hydroxy-3-methylbenzyl) acrylamide and N- (4-hydroxy-2-methyl-5-methylthiobenzyl) acrylamide.
3. A marine antifouling paint according to claim 1, wherein the pigment is red iron oxide.
4. A marine antifouling paint according to claim 1, wherein said filler is at least one selected from zinc oxide, zeolite, fumed silica, organic bentonite, and titanium dioxide.
5. A marine antifouling paint according to claim 1, wherein the solvent is at least one selected from xylene, cyclohexanone, dimethyl phthalate, butyl acetate, and n-butanol.
6. A marine antifouling paint according to claim 1, wherein the auxiliary agent is at least one of a dispersant and a leveling agent.
7. A marine antifouling paint according to claim 6, wherein the dispersant is BYK-P104 or BYK-163, and the leveling agent is 3033 or BYK-306.
8. A marine antifouling paint according to claim 1, which is prepared from the following components in percentage by weight: 30-50% of acrylic resin, 2-10% of iron oxide red, 2-5% of fumed silica, 1-10% of a composite antifouling agent, 5-20% of xylene, 10-20% of butyl acetate and 2-5% of an auxiliary agent, wherein the acrylic resin is acrylic resin containing eugenol capsaicin derivatives.
9. A process for preparing a marine antifouling paint according to claim 1, characterized by the following steps: fully dispersing the filler and the pigment with the formula amount on a high-speed coating dispersion machine for at least 30min, and grinding until the granularity is less than 50 mu m to obtain a solid mixture; adding the ground solid mixture into a mixed liquid containing a film-forming base material, a combined antifouling agent, an auxiliary agent and a solvent according to the formula amount, uniformly stirring under the action of high-shear stirring, adding the rest solvent, and adjusting the viscosity to be 60 s.
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