CN113214734A - Water-based copper-free netting antifouling paint and preparation method and application thereof - Google Patents

Water-based copper-free netting antifouling paint and preparation method and application thereof Download PDF

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Publication number
CN113214734A
CN113214734A CN202110515264.0A CN202110515264A CN113214734A CN 113214734 A CN113214734 A CN 113214734A CN 202110515264 A CN202110515264 A CN 202110515264A CN 113214734 A CN113214734 A CN 113214734A
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agent
free
copper
antifouling
antifouling paint
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张凯
桂泰江
吴连锋
丛巍巍
张晓莲
汪杰
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Marine Chemical Research Institute Co Ltd
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Marine Chemical Research Institute 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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    • 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
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    • 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
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    • C09D5/1662—Synthetic film-forming substance
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Abstract

The invention discloses a water-based copper-free netting antifouling paint and a preparation method and application thereof, and is characterized in that the antifouling paint is composed of 20-38.2% of film-forming resin, 3-12% of copper-free antifouling agent, 25-30% of pigment filling, 0.5-1.5% of dispersing agent, 1-5% of defoaming agent, 0.5-4% of anti-settling agent, 0.2-3% of film-forming auxiliary agent and 20-49.8% of water. The copper-free antifouling paint for fishing nets has the advantages of being water-based, having the characteristics of low VOC content, being friendly to marine environment, low in toxicity, high in efficiency, strong in stability, good in adhesive force, simple and convenient to construct and the like, and being widely applicable to the surfaces of various fishing nets, net cage and net cover substrates of polyethylene, nylon, ultrahigh molecular weight polyethylene and the like.

Description

Water-based copper-free netting antifouling paint and preparation method and application thereof
Technical Field
The invention relates to the field of antifouling paint, and particularly relates to a water-based copper-free netting antifouling paint and a preparation method and application thereof.
Background
Marine fouling is a worldwide phenomenon that afflicts sailors for a long time, and the essence of marine fouling is economic loss caused by the colonization and multiplication of fouling organisms on natural or artificial equipment. Marine fouling occurs in all sea areas and all sea depths, and is particularly obvious in marine aquaculture industry. The stained fishing net reduces the culture capacity of the net cage, compresses the mesh area and increases the load of the net cage in water flow washing, thereby causing deformation of the cage body, stained organisms can also cause erosion damage to the fishing net, and the service life of the net cage is greatly shortened. Fouling organisms growing on the surface of the net body reduce the mesh area to cause blockage, influence the convection of the internal and external seawater, and hinder nutrient exchange, dissolved oxygen diffusion and metabolic waste discharge, so that the yield of aquatic products is influenced, and the eutrophication of a water area easily causes damage to the environment. The complex biofouling community evolved on the surface of the net material can indirectly cause further deposition, breed bacteria and parasites, reduce the yield of aquatic products, seriously cause dysplasia and even death, and seriously affect economic benefits. In traditional mariculture, the net body needs to be dragged back to the shore periodically for mechanical cleaning, the process consumes manpower and material resources, the culture period is influenced, and the culture cost is greatly increased.
At present, methods such as physical removal, use of antifouling agents and biological control are commonly used in the marine aquaculture industry to control biofouling. The physical removal method usually adopts a plurality of methods such as regularly changing nets, mechanically cleaning, antifouling or rotating cage design, chemical control agent and the like to solve the problem of fouling of the fishing net, and has the disadvantages of complicated process, high labor intensity, time waste and labor waste. The use of biocontrol technology to solve the problem of marine biofouling has great potential market value, but the high cost limits its application in the mariculture industry. The current mainstream antifouling method is to use the netting antifouling paint, the antifouling paint is coated on the fishing net by a dip-coating mode, and the antifouling effective period of the fishing net in mariculture is required to be at least six months.
The toxicity of copper to marine fouling organisms is quite dramatic, and the increase in the amount of copper-containing antifouling paints is considered to be the main cause of the increase in copper content in water bodies, and the European Union proposed classification of copper as a hazardous substance of the R50/R53 class based on the 67/548/EEC directive. This suggests that copper may be a potential risk to marine life and the aquatic environment, and copper based fungicides may be banned from use in the field of fishing net antifouling. With the demand of marine environment protection, low copper or no copper, low VOC content and water-based property are the main directions for the future development of antifouling paint for marine aquaculture.
Most of the water-based fishing net antifouling paints on the market realize antifouling efficiency by using a large amount of copper antifouling fillers, and the antifouling paints have high solid content, high specific gravity, easy bottom sinking, poor emulsion stability and no environmental protection requirement.
Disclosure of Invention
The invention aims to avoid the use of copper biocides in netting antifouling paint, select a broad-spectrum, high-efficiency and low-toxicity composite organic antifouling agent system and reduce the pollution of copper to the marine environment. The water-based acrylic acid and polyurethane mixture is used as film-forming resin, the coating has excellent flexibility and wear resistance after being cured, and has strong adhesive capacity on the surfaces of low-polarity netting materials such as nylon, polyethylene, ultra-high molecular weight polyethylene and the like.
In order to achieve the purpose, the invention provides a water-based copper-free netting antifouling paint which comprises 20-38.2% of film-forming resin, 3-12% of copper-free antifouling agent, 25-30% of pigment filling, 0.5-1.5% of dispersing agent, 1-5% of defoaming agent, 0.5-4% of anti-settling agent, 0.2-3% of film-forming assistant and 20-49.8% of water;
further, the film-forming resin is a mixture of waterborne aliphatic polyester polyurethane resin and waterborne acrylic resin emulsion, and the weight ratio of the waterborne aliphatic polyester polyurethane resin to the waterborne acrylic resin emulsion is 10: 0.5-10;
further, the copper-free antifouling agent is one or more of medetomidine, sodium pyrithione, zinc pyrithione, dinitrile tetrachlorobenzene, bromopyrrolecarbonitrile or isothiazolinone;
further, the filling pigment is one or more of carbon black, titanium white, permanent red, zinc oxide, lemon yellow, molybdate orange, phthalocyanine blue, sun-proof yellow, iron oxide black, iron oxide red or toluidine red;
further, the dispersant is one of polyacrylic copolymer potassium salt, polycarboxylic acid sodium salt or polyacrylic acid ammonium salt;
further, the defoaming agent is one of mineral oil hydrophobic fumed silica and metallic soaps, polyether siloxane copolymer or polyether modified polydimethylsiloxane copolymer;
further, the film-forming assistant is one of decaglycol ester or dodecanol ether.
The content of the film-forming resin is controlled to be between 20 and 38.2 percent, and the content of the film-forming resin below the range can cause the reduction of the mechanical property of the antifouling coating and easily generate the phenomena of cracking, falling off and the like, thereby influencing the adhesion of the coating; whereas exceeding this range reduces the antifouling properties of the coating. Too little dispersant and anti-settling agent can not fully disperse the antifouling agent and the pigment in the system, and the storage performance of the coating can not be ensured, while too much dispersant and anti-settling agent can affect the antifouling performance of the coating. The content of the filling pigment is controlled to be 25-30%, so that the filling pigment can be well mixed with the matrix resin, the more proper seepage rate of antifouling components is kept, and the better antifouling performance is exerted.
The preparation method of the water-based copper-free netting antifouling paint comprises the following steps: (1) weighing film-forming resin, a copper-free antifouling agent, a pigment filling agent, a defoaming agent, an anti-settling agent, a film-forming auxiliary agent, a solvent and water according to weight percentage;
(2) grinding color paste: adding water, the compounded copper-free antifouling agent, the filling pigment and the dispersing agent into a container in sequence under low-speed stirring, uniformly mixing, and grinding the mixture by using a basket type sand mill at the rotating speed of 1500 rpm until the fineness is qualified.
(3) Preparing a coating: and (3) adding the film-forming resin, the defoaming agent, the anti-settling agent and the film-forming auxiliary agent into the color paste prepared in the step (2) in sequence at the rotating speed of 500 rpm, adding water for adjusting viscosity, mixing uniformly and filtering.
The water-based copper-free netting antifouling paint can be applied to the surfaces of polyethylene, nylon and ultrahigh molecular weight polyethylene netting materials.
The invention has the beneficial effects that: the water-based copper-free netting antifouling paint disclosed by the invention adopts a mixture of water-based acrylic emulsion and water-based polyurethane emulsion as film-forming resin, has good flexibility and wear resistance, and is suitable for the surfaces of low-polarity flexible nets such as nylon, polyethylene, ultrahigh molecular weight polyethylene and the like. The polyurethane and the base material greatly improve the adhesive force of the coating on the surface of the net material through intermolecular hydrogen bonds. Compared with solvent-based coatings, the water-based coatings meet the environmental protection requirement better. The low-toxicity and high-efficiency copper-free antifouling filler is selected, harmful substances such as copper which has potential harm to marine ecological environment are not contained, the addition amount of the antifouling paint is small, the influence on the stability of the emulsion is reduced, and the storage stability of the antifouling paint is improved. The coating can be attached to the surface of the base material within 5 minutes by dip coating, is simple and convenient to use, does not contain organic volatile matters, is harmless to constructors, and can be dried and cured at normal temperature. The coating has good adhesion to fishing gears such as fishing nets, netting and the like, has excellent flexibility and wear resistance after being completely cured, does not crack or peel after being bent, and can ensure the antifouling period of 8-12 months.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, specific embodiments of the present invention are described in detail below.
Example 1
1. The following components (calculated by the total weight percentage of the antifouling paint) were weighed:
Figure BDA0003061725590000031
2. grinding color paste
And sequentially adding part of water, weighed zinc pyrithione, bromopyrrole carbonitrile, iron oxide red and polyacrylic acid copolymer sylvite into a container at the normal temperature under the stirring of 600 revolutions per minute, fully and uniformly stirring, transferring to a basket type sand mill, and grinding the mixture at the rotating speed of 1500 revolutions per minute until the fineness is less than or equal to 60 mu m.
3. Preparation of the coating
And at normal temperature, sequentially adding weighed water-based aliphatic polyester polyurethane resin, water-based acrylic emulsion, polyether siloxane copolymer, polyvinyl alcohol and glycol ester into the prepared color paste at the rotating speed of 500 revolutions per minute of a stirrer, fully and uniformly dispersing, and finally adding the rest of water for blending, thus preparing the water-based copper-free mesh antifouling paint.
Example 2
The preparation process is the same as that of example 1, and the raw material formula is as follows (calculated by the total weight percentage of the antifouling paint):
Figure BDA0003061725590000041
example 3
The preparation process is the same as that of example 1, and the raw material formula is as follows (calculated by the total weight percentage of the antifouling paint):
Figure BDA0003061725590000042
Figure BDA0003061725590000051
example 4
The preparation process is the same as that of example 1, and the raw material formula is as follows (calculated by the total weight percentage of the antifouling paint):
Figure BDA0003061725590000052
example 5
The preparation process is the same as that of example 1, and the raw material formula is as follows (calculated by the total weight percentage of the antifouling paint):
Figure BDA0003061725590000053
the water-based copper-free netting antifouling paint disclosed by the invention is constructed by dip coating, and is subjected to conventional performance test. The adhesive force is tested and evaluated by adopting the following method and evaluation standard:
adhesive force: the fishing net coated with the antifouling paint and completely dried is folded back and forth for 25 times, and the surface coating of the fishing net is observed by naked eyes: the adhesive force is evaluated to be grade 1 if no drop or crack exists; the adhesive force is evaluated as grade 2 if the paint has slight cracks and does not fall off; if the adhesive force falls off slightly, the adhesive force is evaluated as 3 grades; and if the cracks and the falling are obvious, the adhesive force is evaluated to be 4 grades.
Secondly, antifouling period effect: and (4) evaluating the antifouling performance after the real sea is hung on the net. The antifouling paint is considered to be effective if the marine fouling adhesion area on the netting is less than 10%.
Storage stability: the paint is placed for 15 days at the temperature of 60 ℃, the paint is not caked, and the paint can be uniformly stirred after precipitation without coarsening.
The application test results of each embodiment of the water-based copper-free netting antifouling paint are as follows:
serial number Adhesion force Antifouling period effect Storage stability
Example 1 Level 1 12 months old By passing
Example 2 Level 1 12 months old By passing
Example 3 Level 1 12 months old By passing
Example 4 Level 1 For 10 months By passing
Example 5 Level 1 8 months old By passing
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The water-based copper-free netting antifouling paint is characterized by comprising a film-forming resin and a copper-free antifouling agent, wherein the system simultaneously comprises a filling pigment, a solvent and various additives, and the weight percentages of the components are as follows:
20 to 38.2 percent of film-forming resin
3 to 12 percent of copper-free antifouling agent
25 to 30 percent of filling pigment
0.5 to 1.5 percent of dispersant
1 to 5 percent of defoaming agent
0.5 to 4 percent of anti-settling agent
0.2 to 3 percent of film forming additive
20-49.8% of water.
2. The aqueous copper-free netting antifouling paint of claim 1, wherein: the film-forming resin is a mixture of waterborne aliphatic polyester polyurethane resin and waterborne acrylic resin emulsion, and the weight ratio of the waterborne aliphatic polyester polyurethane resin to the waterborne acrylic resin emulsion is 10: 0.5-10.
3. The aqueous copper-free netting antifouling paint of claim 1, wherein: the copper-free antifouling agent is one or more of medetomidine, sodium pyrithione, zinc pyrithione, dinitrile tetrachlorobenzene, bromopyrrolecarbonitrile or isothiazolinone.
4. The aqueous copper-free netting antifouling paint of claim 1, wherein: the filling pigment is one or more of carbon black, titanium white, permanent red, zinc oxide, lemon yellow, molybdate orange, phthalocyanine blue, sun-proof yellow, iron oxide black, iron oxide red or toluidine red.
5. The aqueous copper-free netting antifouling paint of claim 1, wherein: the dispersing agent is one of polyacrylic copolymer potassium salt, polycarboxylic acid sodium salt or polyacrylic acid ammonium salt.
6. The aqueous copper-free netting antifouling paint of claim 1, wherein: the defoaming agent is one of mineral oil hydrophobic fumed silica and metallic soaps, polyether siloxane copolymers or polyether modified polydimethylsiloxane copolymers.
7. The aqueous copper-free netting antifouling paint of claim 1, wherein: the anti-settling agent is one of sodium alginate, methyl cellulose ether, polyvinyl alcohol, modified urea polyurethane or modified polyurea.
8. The aqueous copper-free netting antifouling paint of claim 1, wherein: the film-forming assistant is one of decaglycol ester or dodecanol ether.
9. A method for preparing the water-based copper-free netting antifouling paint of any one of claims 1 to 8, characterized in that:
(1) weighing film-forming resin, a copper-free antifouling agent, a pigment filling agent, a defoaming agent, an anti-settling agent, a film-forming auxiliary agent, a solvent and water according to weight percentage;
(2) grinding color paste
Adding water, the compounded copper-free antifouling agent, the filling pigment and the dispersing agent into a container in sequence under low-speed stirring, uniformly mixing, and grinding the mixture by using a basket type sand mill at the rotating speed of 1500 rpm until the fineness is qualified.
(3) Preparation of the coating
And (3) adding the film-forming resin, the defoaming agent, the anti-settling agent and the film-forming auxiliary agent into the color paste prepared in the step (2) in sequence at the rotating speed of 500 rpm, adding water for adjusting viscosity, mixing uniformly and filtering.
10. Use of the coating according to any one of claims 1 to 8, comprising dip-coating the coating according to any one of claims 1 to 8 on the surface of a polyethylene, nylon, ultra high molecular weight polyethylene netting material, and drying and curing to form a stain resistant layer.
CN202110515264.0A 2021-05-12 2021-05-12 Water-based copper-free netting antifouling paint and preparation method and application thereof Pending CN113214734A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110540803A (en) * 2019-08-30 2019-12-06 海洋化工研究院有限公司 Cuprous oxide-free high-flexibility water-based cage antifouling paint

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110540803A (en) * 2019-08-30 2019-12-06 海洋化工研究院有限公司 Cuprous oxide-free high-flexibility water-based cage antifouling paint

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