CN112574629B - Water-based antifouling paint and application thereof - Google Patents
Water-based antifouling paint and application thereof Download PDFInfo
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- CN112574629B CN112574629B CN202011460656.3A CN202011460656A CN112574629B CN 112574629 B CN112574629 B CN 112574629B CN 202011460656 A CN202011460656 A CN 202011460656A CN 112574629 B CN112574629 B CN 112574629B
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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
- C09D133/04—Homopolymers or copolymers of esters
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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
-
- 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
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
Abstract
The invention provides a water-based antifouling paint and application thereof, belonging to the technical field of paints. The paint comprises the following components in parts by weight: 34-69 parts of water-based acrylic resin, 1-69 parts of water-based fluorine-silicon modified acrylic resin, 3-6 parts of nano filler, 5-23 parts of fluorinated solid additive, 4-44 parts of diluent, 2-20 parts of curing agent and 1-7 parts of film-forming additive. In the invention, the use of the water-based acrylic resin and the nano filler ensures that the coating has basic antifouling effect; the water-based fluorine-silicon modified acrylic resin can generate electricity by friction under the action of waves, generated charges are loaded on a coating film formed by the coating, and the existence of the charges can inhibit microorganisms from being loaded on the surface of the coating film, so that the pollution degree of the coating is reduced; meanwhile, the use of the fluorinated solid additive further improves the triboelectric charging property of the coating and is beneficial to inhibiting the growth of microorganisms. The data of the examples show that: the water-based antifouling paint has a good antifouling effect.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based antifouling coating and application thereof.
Background
The antifouling coating can be used as a protective coating to inhibit the adhesion of plankton in water on the surface of the coating. With the increasing requirement of environmental protection, the waterborne antifouling coating becomes the trend of the development of antifouling coatings. Waterborne low surface energy coatings can reduce the adhesion of aquatic organisms by virtue of their low surface energy properties.
The anti-fouling coating in the water environment can generate friction current under the impact of water flow, and researches find that the friction generator manufactured by utilizing the principles of friction electrification and electrostatic induction can effectively collect friction energy and convert the friction energy into electric energy to supply energy to the miniature electronic device. If the friction electric energy can be collected and utilized, the energy pressure can be greatly relieved, and great economic benefits can be generated. Researchers have developed various forms of friction generators to realize the collection and utilization of friction energy. These triboelectric energies can reduce the adhesion of aquatic organisms on the coating and enhance antifouling properties.
The water-based low-surface-energy antifouling friction power generation coating is an important protective material for marine ships and equipment, and the antifouling effect of the antifouling coating plays an important role in saving the sailing speed and energy of the ships.
In the prior art, the antifouling paint mainly realizes the antifouling effect based on adding antifouling filler, the antifouling principle is single, and the antifouling effect needs to be improved.
Disclosure of Invention
In view of the above, the present invention aims to provide an aqueous antifouling paint and an application thereof, wherein the aqueous antifouling paint provided by the present invention has an excellent antifouling effect.
The invention provides a water-based antifouling paint which comprises the following components in parts by weight:
preferably, the nano filler is one or more of silicon dioxide, silane modified silicon dioxide, fluorine modified silicon dioxide, silane modified titanium dioxide, fluorine modified titanium dioxide, silane modified zinc oxide and fluorine modified zinc oxide.
Preferably, the nano filler is formed by mixing a nano filler with the particle size of 30-50 nm and a nano filler with the particle size of 50-200 nm according to the volume ratio of (1: 10) - (10: 1).
Preferably, the nano filler is prepared by mixing nano silicon dioxide with the particle size of 40nm and the particle size of 150nm according to a volume ratio of 2: 1 are mixed.
Preferably, the fluorinated solid additive is one or more of graphite fluoride, fluorinated paraffin and fluorinated montmorillonite.
Preferably, the particle size of the fluorinated solid additive is 10-200 μm.
Preferably, the diluent is one or more of water, ethanol and n-butanol.
Preferably, the curing agent is a waterborne isocyanate curing agent.
Preferably, the film forming aid is one or more of a dispersant, a defoamer and a coupling agent.
The invention also provides application of the water-based antifouling paint in the technical scheme in the field of metal substrate protection, wherein the metal substrate is in a water environment.
The invention provides a water-based antifouling paint which comprises the following components in parts by weight: 34-69 parts of water-based acrylic resin, 1-69 parts of water-based fluorine-silicon modified acrylic resin, 3-6 parts of nano filler, 5-23 parts of fluorinated solid additive, 4-44 parts of diluent, 2-20 parts of curing agent and 1-7 parts of film-forming additive. In the invention, the use of the water-based acrylic resin and the nano filler ensures that the coating has basic antifouling effect. The water-based fluorine-silicon modified acrylic resin can generate electricity by friction under the action of waves, generated charges are loaded on a coating film formed by the coating, and the existence of the charges can inhibit microorganisms from being loaded on the surface of the coating film, so that the pollution degree of the coating is reduced; meanwhile, the use of the fluorinated solid additive further improves the triboelectric charging property of the coating and is beneficial to inhibiting the growth of microorganisms. The data of the examples show that: the water-based antifouling paint has a good antifouling effect.
Detailed Description
The invention provides a water-based antifouling paint which comprises the following components in parts by weight:
in the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The water-based antifouling paint provided by the invention comprises 34-69 parts by mass of water-based acrylic resin, preferably 35-65 parts by mass, more preferably 40-60 parts by mass, and more preferably 45-55 parts by mass; in the embodiment of the present invention, the weight part of the aqueous acrylic resin is preferably 40 parts, 45 parts or 55 parts. In the present invention, the aqueous acrylic resin enables the coating to form a continuous film layer.
Based on the weight parts of the water-based acrylic resin, the water-based antifouling paint provided by the invention comprises 1-69 parts of water-based fluorine-silicon modified acrylic resin by mass, preferably 5-60 parts, more preferably 10-50 parts, and more preferably 20-40 parts; in a specific embodiment of the present invention, the weight part of the aqueous fluorosilicone modified acrylic resin is preferably 5 parts, 10 parts, 20 parts or 30 parts. In the invention, due to the existence of fluorine and silicon, the aqueous fluorosilicone modified acrylic resin can generate electricity by friction under the action of waves, the generated charges are loaded on a coating formed by the coating, and the existence of the charges can inhibit microorganisms from being loaded on the surface of the coating, thereby further slowing down the pollution degree of the coating.
The water-based antifouling paint provided by the invention comprises 3-6 parts by weight of nano filler, preferably 4-5 parts by weight, based on the weight parts of the water-based acrylic resin, and in the specific embodiment of the invention, the weight parts of the nano filler are preferably 5 parts, 6 parts and 3 parts. In the invention, the nano filler is preferably formed by mixing a nano filler with the particle size of 30-50 nm and a nano filler with the particle size of 50-200 nm according to the volume ratio of (1: 10) - (10: 1). In the present invention, the nanofiller is preferably one or more of silica, silane-modified silica, fluorine-modified silica, silane-modified titania, fluorine-modified titania, silane-modified zinc oxide, and fluorine-modified zinc oxide, more preferably silica, and even more preferably silica VK-SP 30G. In a specific embodiment of the present invention, the nano filler is specifically preferably nano silica having a particle size of 40nm and a particle size of 150nm in a volume ratio of 2: 1 are mixed. In the invention, the function of the nano filler is to enable the coating to have certain roughness, thereby improving the antifouling property of the coating.
Based on the weight parts of the water-based acrylic resin, the water-based antifouling paint provided by the invention comprises 5-23 parts of fluorinated solid additive, preferably 10-20 parts, and more preferably 15 parts; in a particular embodiment of the invention, the fluorinated solid additive is preferably present in an amount of 10 parts or 15 parts by weight. In the present invention, the fluorinated solid additive is preferably one or more of graphite fluoride, fluorinated paraffin and fluorinated montmorillonite, and is further preferably graphite fluoride; the particle size of the fluorinated solid additive is preferably 10-200 μm, and more preferably 10-50 μm. In the present invention, the fluorinated solid additive functions to increase the surface hydrophobicity of the coating.
The water-based antifouling paint provided by the invention comprises 4-44 parts by weight of diluent, preferably 8-40 parts by weight, more preferably 10-20 parts by weight, based on the parts by weight of the water-based acrylic resin, and in the specific embodiment of the invention, the diluent is preferably 10 parts by weight, 5 parts by weight, 4 parts by weight, 12 parts by weight or 7 parts by weight; the diluent is preferably one or more of water, ethanol and n-butanol, and is more preferably water. In the invention, the diluent can reduce the viscosity of the coating and facilitate the coating construction.
Based on the weight parts of the waterborne acrylic resin, the waterborne antifouling paint provided by the invention comprises 2-20 parts of a curing agent, preferably 3-10 parts, and further preferably 5-8 parts; in specific embodiments of the present invention, the curing agent is preferably 2 parts, 3 parts, or 5 parts by weight. (ii) a The curative is preferably a waterborne isocyanate curative, and in a particular embodiment of the invention, the curative is preferably Bayhydur XP 2655. In the present invention, the curing agent functions to increase the degree of crosslinking of the coating.
Based on the weight parts of the water-based acrylic resin, the water-based antifouling paint provided by the invention comprises 1-7 parts of film-forming additive, preferably 3-5 parts; in a particular embodiment of the invention, the film-forming aid is preferably present in an amount of 2, 3 or 5 parts by weight; the film-forming assistant is preferably one or more of a dispersant, a defoaming agent and a coupling agent, and is more preferably a dispersant. In the invention, the dispersant is preferably Dispex AA 4040 or BYK190, more preferably Dispex AA 4040, and the weight part of the dispersant is preferably 2-5 parts, particularly preferably 2 parts, 3 parts or 5 parts based on the weight part of the aqueous acrylic resin. In the present invention, the antifoaming agent is preferably BYK028, BYK012, and BYK 024; the weight part of the defoaming agent is preferably 2-5 parts based on the weight part of the water-based acrylic resin. In the invention, the coupling agent is preferably KH550, KH560 and KH570, and the weight part of the coupling agent is preferably 2-5 parts based on the weight part of the aqueous acrylic resin. In the present invention, the film-forming assistant can improve the surface flatness after film formation.
The preparation method of the water-based antifouling paint is not particularly limited, and a mixture preparation method well known to those skilled in the art can be adopted.
The invention also provides application of the water-based antifouling paint in the technical scheme in the field of metal substrate protection, wherein the metal substrate is in a water environment. In the present invention, the metal substrate preferably comprises a marine vessel, an offshore metal structure installation, a marine facility underwater oleophobic tubing, or an offshore drilling platform.
In the invention, after the water-based antifouling paint is coated on a metal substrate, under wave friction, the surface of a coating formed by the water-based antifouling paint can generate electricity by friction, and the generated charges can inhibit the growth of microorganisms on the surface of the coating, thereby endowing the coating with antifouling property.
The following examples are provided to illustrate the water-based antifouling paint and the application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
The nano filler is prepared from nano silicon dioxide VK-SP30G with the particle size of 40nm and the particle size of 150nm according to the volume ratio of 2: 1 are mixed.
Example 2
The nano filler is prepared from nano silicon dioxide with the particle size of 40nm and the particle size of 150nm according to the volume ratio of 2: 1 are mixed.
Example 3
The nano-filler is prepared from nano-silica VK-SP30G with the particle size of 40nm and the particle size of 150nm according to the volume ratio of 2: 1 are mixed.
Example 4
The nano-filler is prepared from nano-silica VK-SP30G with the particle size of 40nm and the particle size of 150nm according to the volume ratio of 2: 1 are mixed.
Example 5
The nano-filler is prepared from nano-silica VK-SP30G with the particle size of 40nm and the particle size of 150nm according to the volume ratio of 2: 1 are mixed.
Example 6
Similar to example 1, except that the weight portion of the aqueous fluorosilicone modified acrylic resin is 10.
Example 7
Similar to example 1, except that the weight portion of the aqueous fluorosilicone modified acrylic resin is 5.
Example 8
Similar to example 1, except that the nanofiller was prepared from nanosilica having a particle size of 40nm and a particle size of 150nm in a volume ratio of 1: 10 are mixed together.
Comparative example 1
Similar to example 1, except that the aqueous fluorosilicone-modified acrylic resin was not added.
Comparative example 2
Similar to example 1, except that the nanofiller was silica having a particle size of 10 nm.
Comparative example 3
Similar to example 1, except that no nanofiller was added.
The antifouling property of the obtained coating material was tested by GB-5370-2007, and the results are shown in Table 1.
TABLE 1 antifouling results of coating films obtained from the aqueous antifouling paints obtained in examples 1 to 8 and comparative examples 1 to 3
As can be seen from table 1: when the proportion of the aqueous fluorosilicone modified acrylic resin which is easy to generate frictional charges is increased to 30 parts, the antifouling effect of the obtained coating is good, because the fluorosilicone group in the aqueous fluorosilicone modified acrylic resin has the characteristic of low surface energy, marine plankton is not used for being attached to the coating, and meanwhile plankton adhered to the coating with the low surface energy under the washing of water flow is more easily washed away, so that the coating has good antifouling performance; with the increase of the using amount of the nano particles in the coating, microstructures are generated on the surface of the coating due to the aggregation of the nano particles, the microstructures increase the water contact angle of the coating and reduce the contact area of water and the coating, so that the contact area of plankton and the coating is reduced, and the antifouling performance of the coating is improved.
The triboelectrification of the obtained aqueous antifouling coating was measured by a solid-liquid triboelectrification method, and the results are shown in table 2.
TABLE 2 triboelectrification characteristics of coating films obtained from the aqueous antifouling paints obtained in examples 1 to 8 and comparative examples 1 to 3
As can be seen from table 2: when the proportion of the water-based fluorine-silicon modified acrylic resin is increased, the quantity of fluorine-silicon groups on the surface of the coating is increased, and the coating surface is provided with corresponding charges due to electron transfer in the friction process of the fluorine-silicon groups and water. The fluorine silicon groups on the surface of the coating are increased, and the more charges are generated on the surface after the coating is rubbed with water. These charges can inhibit the enrichment of plankton on the surface of the coating in water, thereby improving the antifouling performance of the coating. When the using amount of the nano particles in the coating is increased to 6 parts, more microstructures are generated on the surface of the obtained coating, and the microstructures are combined with the fluorine-silicon modified acrylic resin with low surface energy, so that the water contact angle of the surface of the coating is increased, higher friction current density is generated on the surface of the coating, and the surface charges can inhibit the attachment of plankton on the surface of the coating and improve the antifouling performance of the coating.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. The water-based antifouling paint is characterized by comprising the following components in parts by weight:
40 parts of water-based acrylic resin;
30 parts of water-based fluorine-silicon modified acrylic resin;
5 parts of nano filler;
15 parts of graphite fluoride;
5 parts of water;
curing agent Bayhydur XP 26552 parts;
dispex AA 40403 parts of a dispersant;
the nano filler is prepared from nano silicon dioxide with the particle size of 40nm and the particle size of 150nm according to the volume ratio of 2: 1, mixing;
the particle size of the graphite fluoride is 15 mu m.
2. Use of an aqueous antifouling coating according to claim 1 in the field of protection of metal substrates, characterized in that the metal substrates are in an aqueous environment.
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| CN112574629B true CN112574629B (en) | 2021-11-12 |
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| CN1771445A (en) * | 2004-04-14 | 2006-05-10 | Lg化学株式会社 | Anti-reflective coating composition and coating film with excellent stain resistance |
| CN107022296A (en) * | 2017-04-07 | 2017-08-08 | 中国科学院兰州化学物理研究所 | A kind of collection of energy coating material and its application based on triboelectrification |
| CN110698936A (en) * | 2019-10-18 | 2020-01-17 | 成都普瑞斯特新材料有限公司 | Pure water self-cleaning coating and preparation method thereof |
| CN111040495A (en) * | 2019-12-26 | 2020-04-21 | 中国科学院兰州化学物理研究所 | Anti-biofouling triboelectric power generation coating material and preparation method and application thereof |
| CN111944087A (en) * | 2020-07-22 | 2020-11-17 | 广州工程技术职业学院 | Fluorosilicone hybrid water-based acrylate emulsion and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190118221A1 (en) * | 2017-10-24 | 2019-04-25 | The Boeing Company | Conformal fluoropolymer coatings |
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- 2020-12-11 CN CN202011460656.3A patent/CN112574629B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1771445A (en) * | 2004-04-14 | 2006-05-10 | Lg化学株式会社 | Anti-reflective coating composition and coating film with excellent stain resistance |
| CN107022296A (en) * | 2017-04-07 | 2017-08-08 | 中国科学院兰州化学物理研究所 | A kind of collection of energy coating material and its application based on triboelectrification |
| CN110698936A (en) * | 2019-10-18 | 2020-01-17 | 成都普瑞斯特新材料有限公司 | Pure water self-cleaning coating and preparation method thereof |
| CN111040495A (en) * | 2019-12-26 | 2020-04-21 | 中国科学院兰州化学物理研究所 | Anti-biofouling triboelectric power generation coating material and preparation method and application thereof |
| CN111944087A (en) * | 2020-07-22 | 2020-11-17 | 广州工程技术职业学院 | Fluorosilicone hybrid water-based acrylate emulsion and preparation method and application thereof |
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