Long-acting bionic antimicrobial functional coating as well as preparation method and application thereof

Abstract

The invention provides a long-acting bionic antimicrobial functional coating as well as a preparation method and application thereof, and relates to the technical field of marine coatings, the long-acting bionic antimicrobial functional coating comprises a component A and a component B, the component A is prepared from the following raw materials: silanol-terminated polydimethylsiloxane, methyl phenyl polysiloxane, a methylhydrosiloxane-dimethyl siloxane copolymer, an auxiliary agent and an organic solvent a; and the component B comprises the following raw materials: ethyl silicate and an organic solvent b. According to the long-acting bionic antimicrobial functional coating provided by the invention, marine organisms cannot be attached to the surface of a ship body or easily fall off, so that the antifouling effect is achieved, and the pollution path of antifouling paint to the marine environment is fundamentally cut off.

Description

Technical Field

[0001] This invention relates to the field of marine coating technology, and in particular to a long-lasting biomimetic antimicrobial functional coating, its preparation method, and its application. Background Technology

[0002] Traditional self-polishing antifouling paints are chemically exudative antifouling coatings with cuprous oxide as the main biocide, namely the modern self-polishing copolymer (SPC) system. These coatings release copper ions and other bioactive substances through controlled dissolution of the paint film surface under seawater conditions, thereby inhibiting the attachment of marine organisms. However, copper ions are heavy metal pollutants that easily accumulate in port and coastal waters, are difficult to degrade, and may have toxic effects on non-target aquatic organisms such as juvenile fish and shellfish, thus affecting the local ecosystem balance. Regions with strict environmental requirements, such as California and Washington State in the United States, and the European Union, have begun to restrict or even ban the use of copper-containing antifouling paints on yachts and in certain waters. This trend is gradually expanding globally. Therefore, the market urgently needs a new antifouling technology that does not rely on toxic biocides to meet increasingly stringent environmental protection requirements.

[0003] In view of this, the present invention is hereby proposed. Summary of the Invention

[0004] One of the objectives of this invention is to provide a long-lasting biomimetic antimicrobial functional coating to at least solve one of the technical problems existing in the prior art. The long-lasting biomimetic antimicrobial functional coating provided by this invention can prevent marine organisms from adhering to the surface of the ship hull or make them easily detach, thereby achieving an antifouling effect and fundamentally cutting off the pollution pathway of antifouling paint to the marine environment.

[0005] The second objective of this invention is to provide a method for preparing a long-lasting biomimetic antimicrobial functional coating.

[0006] The third objective of this invention is to provide a long-lasting biomimetic antimicrobial functional coating or the application of a long-lasting biomimetic antimicrobial functional coating prepared by the aforementioned preparation method in the preparation of a long-lasting biomimetic antimicrobial functional coating.

[0007] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: In a first aspect, the present invention provides a long-lasting biomimetic antimicrobial functional coating, comprising: component A and component B; Component A includes the following raw materials: silanol-terminated polydimethylsiloxane, methylphenyl polysiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, additives, and organic solvent a; Component B includes the following raw materials: ethyl silicate and organic solvent b.

[0008] Furthermore, the volume ratio of component A to component B is 7~9:1.

[0009] Furthermore, the additives include defoamers, antisettling agents, pigments, and silane coupling agents.

[0010] Furthermore, the raw materials of component A, by mass percentage, include: 14%~20% methylphenyl polysiloxane, 14%~20% methylhydrosiloxane-dimethylsiloxane copolymer, 1%~3% defoamer, 1%~3% anti-settling agent, 8%~12% organic solvent a, 2%~4% silane coupling agent, and 14%~20% pigment, and the balance being silanol-terminated polydimethylsiloxane; Preferably, the viscosity of the silanol-terminated polydimethylsiloxane is 1000~20000 mPa·s; Preferably, the molecular weight of the methylhydrosiloxane-dimethylsiloxane copolymer is 1000-5000 g / mol; Preferably, the organic solvent a comprises xylene and / or trimethylbenzene; Preferably, the pigment includes one or more of iron oxide red, scarlet powder, phthalocyanine blue, and phthalocyanine green.

[0011] Furthermore, the raw materials of component A, by mass percentage, include: 17% methylphenyl polysiloxane, 17% methylhydrosiloxane-dimethylsiloxane copolymer, 2% defoamer, 2% anti-settling agent, 10% organic solvent a, 3% silane coupling agent, and 17% pigment, and the balance being silanol-terminated polydimethylsiloxane.

[0012] Furthermore, the raw materials of component B, by mass percentage, include: 50%-60% ethyl silicate and the balance organic solvent b; Preferably, the organic solvent b includes xylene and / or trimethylbenzene.

[0013] Furthermore, the raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% organic solvent b.

[0014] Secondly, the present invention provides a method for preparing a long-lasting biomimetic antimicrobial functional coating, comprising: mixing component A and component B to obtain the long-lasting biomimetic antimicrobial functional coating; Component A is prepared by mixing silanol-terminated polydimethylsiloxane, methylphenyl polysiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, additives and organic solvent a. Component B is prepared by mixing ethyl silicate and organic solvent b.

[0015] Furthermore, component A is prepared through the following steps: (a) Mix the anti-settling agent, defoamer and part of organic solvent a to form a matrix slurry; (b) Add pigment to the matrix slurry to obtain a color paste; (c) Grinding the pigment paste; (d) The ground color paste, silanol-terminated polydimethylsiloxane and methylphenyl polysiloxane are mixed, and then methylhydrosiloxane-dimethylsiloxane copolymer and silane coupling agent are added to obtain component A; Preferably, the stirring time in step (a) is 10-15 minutes; Preferably, the stirring time in step (b) is 30-45 minutes; Preferably, in step (c), the fineness of the pigment paste after the grinding process is ≤25μ; Preferably, in the preparation of component A, after the main resin mixing is completed, the process further includes: cleaning the production equipment with the reserved organic solvent a, reusing the cleaning solution, adjusting the viscosity as needed, and finally obtaining component A; Preferably, component B is prepared by the following steps: mixing ethyl silicate and organic solvent b, and then filtering through an 80-120 mesh filter to obtain component B.

[0016] Thirdly, the present invention provides a long-lasting biomimetic antimicrobial functional coating or the application of a long-lasting biomimetic antimicrobial functional coating prepared by the aforementioned preparation method in the preparation of a long-lasting biomimetic antimicrobial functional coating.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The long-lasting biomimetic antimicrobial functional coating provided by this invention adopts a two-component system consisting of component A and component B. Component A contains silanol-terminated polydimethylsiloxane as the main chain polymer, combined with methylphenyl polysiloxane to improve the toughness of the paint film, and methylhydrosiloxane-dimethylsiloxane copolymer containing Si-H bonds as a crosslinking reinforcing component, which, together with additives and organic solvent a, constitutes a stable premix. Component B uses ethyl silicate as the core crosslinking agent and is uniformly mixed with organic solvent b, so that the two components remain in a stable storage state before construction. When used, after being mixed in proportion, a condensation reaction can be rapidly carried out to construct a dense three-dimensional crosslinked silicon-oxygen network in situ.

[0018] The long-lasting biomimetic antimicrobial functional coating provided by this invention forms a smooth surface with extremely low surface energy and good elasticity after curing. This effectively inhibits the firm attachment of marine spores and larvae. Even if initial attachment occurs, it is easily detached under the shear force of water currents generated during ship navigation, thus achieving a long-term and stable physical antifouling effect. Simultaneously, the entire system does not rely on the release of cuprous oxide or other toxic biocides, posing no risk of heavy metal pollution and fully complying with increasingly stringent global environmental regulations. Furthermore, the coating possesses excellent weather resistance, crack resistance, and low frictional resistance, significantly reducing ship drag, helping to save fuel consumption and extend maintenance intervals. Detailed Implementation

[0019] Unless otherwise defined herein, the scientific and technical terms used in conjunction with this invention shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms shall be clear; however, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or foreign definitions. In this application, unless otherwise stated, the use of "or" means "and / or". Furthermore, the use of the term "comprising" and other forms is non-limiting.

[0020] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] The first aspect of the present invention provides a long-lasting biomimetic antimicrobial functional coating, comprising: component A and component B; wherein component A comprises the following raw materials: silanol-terminated polydimethylsiloxane, methylphenyl polysiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, additives and organic solvent a; wherein component B comprises the following raw materials: ethyl silicate and organic solvent b.

[0022] In this invention, the reaction mechanism of components A and B is a multi-path condensation and cross-linking process: the main path is the de-alcoholization condensation between the silanol-terminated polydimethylsiloxane of component A and the tetraethyl orthosilicate hydrolysate of component B. The auxiliary path involves the formation of new silanols through moisture curing of the Si-H bonds within component A, which then participate in the main reaction. These reactions collectively construct a dense, cross-linked three-dimensional silicone resin network. This network structure endows the coating with extremely low surface energy, making it difficult for marine organisms (such as barnacles and algae) to adhere firmly, and even if they do, they are easily washed away by water currents during ship navigation, thus achieving the purpose of antifouling.

[0023] The coating provided by this invention is a long-lasting biomimetic antimicrobial functional coating for ships, which utilizes physical defense and employs a completely different antifouling method compared to the chemical attack of self-polishing antifouling paints. Traditional self-polishing antifouling paint films contain hydrolyzable resins and antifouling agents (such as cuprous oxide). Under the action of seawater, the paint film surface slowly and controllably dissolves, continuously exposing new antifouling agents and forming a toxic "surface layer" that prevents marine organisms from attaching. This is fundamentally different from the long-lasting biomimetic antimicrobial functional coating of this invention: the film itself is non-toxic or extremely low in toxicity. Its core is the creation of a surface with a roughness far lower than that of traditional self-polishing antifouling paints and a low surface energy. Although marine organism spores or larvae can temporarily attach, the adhesion is very weak. When the ship reaches a certain speed, the shear force generated by the water flow can easily peel off the organisms.

[0024] In some preferred embodiments, the volume ratio of component A to component B is 7 to 9:1, for example, it can be 7:1, 8:1, 9:1, etc., preferably 8:1.

[0025] In some preferred embodiments, the additives include defoamers, antisettling agents, pigments, and silane coupling agents.

[0026] Preferably, the defoamer is BYK CHEMICAL product model: BYK-052 or Tego product type: Airex 900; Preferably, the anti-settling agent is Zhejiang Fenghong product model: SD-2 or Elementis product model: Bentone® SD-2; Preferably, the pigment includes one or more of iron oxide red, scarlet, phthalocyanine blue, and phthalocyanine green; Preferably, the iron oxide red is Shanghai Yipin Pigment product model: 190 or Hunan Sanhuan Pigment product model: 190; Preferably, the silane coupling agent is Evonik Industries AG product model: DYNASYLAN-DAMO or Wacker product type: GENIOSIL® XL 926.

[0027] In some preferred embodiments, the raw materials of component A, by mass percentage, include: 14-20% methylphenyl polysiloxane (Wacker Chemie AG product model: AK-50), 14-20% methylhydrosiloxane-dimethylsiloxane copolymer (Wacker Chemie AG product model: HC 1107), 1-3% defoamer, 1-3% anti-settling agent, 8-12% organic solvent a, 2-4% silane coupling agent, and 14-20% pigment, and the balance being silanol-terminated polydimethylsiloxane (DowChemical product model: DC-1107).

[0028] Among them, silanol-terminated polydimethylsiloxane is the main polymer that provides the coating with low surface energy, weather resistance and elasticity, and the terminal silanol hydroxyl groups (-Si-OH) are the main active sites involved in curing and crosslinking.

[0029] Wherein, based on the total mass of component A as 100%, the amount of methylphenyl polysiloxane added is 14~20%, for example, it can be 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.; methylphenyl polysiloxane is a modified resin that participates in the overall cross-linking network, making the paint film more tough.

[0030] Wherein, based on the total mass of component A as 100%, the amount of methylhydrosiloxane-dimethylsiloxane copolymer added is 14~20%, for example, it can be 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.; the methylhydrosiloxane-dimethylsiloxane copolymer acts as a crosslinking agent and reinforcing agent to improve the crosslinking density, adhesion and cohesive strength of the coating.

[0031] The amount of defoamer added is 1-3%, based on the total mass of component A as 100%, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, etc.; the defoamer prevents the generation and retention of bubbles, ensuring a smooth and even paint film.

[0032] The amount of anti-settling agent added is 1-3%, based on the total mass of component A as 100%, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, etc.; the anti-settling agent prevents precipitation and clumping during storage and maintains the stability of the formula.

[0033] Wherein, based on the total mass of component A as 100%, the amount of organic solvent a added is 8~12%, for example, it can be 8%, 9%, 10%, 11%, 12%, etc.; In this embodiment, based on the total mass of component A as 100%, the amount of silane coupling agent added is 2-4%, for example, 2%, 2.5%, 3%, 3.5%, 4%, etc. As an adhesion promoter, the silane coupling agent can improve the interfacial bonding performance between the silicone coating and the underlying substrate. It forms chemical bonds at the coating-substrate interface through a hydrolysis-condensation reaction, effectively enhancing the adhesion and durability of the coating, preventing problems such as blistering and peeling caused by interfacial failure in marine environments, thereby ensuring the long-term stable performance of the antifouling function.

[0034] Wherein, based on the total mass of component A as 100%, the amount of pigment added is 14-20%, for example, it can be 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc. The pigment can provide color covering power.

[0035] Preferably, the viscosity of the silanol-terminated polydimethylsiloxane is 1000~20000 mPa·s.

[0036] Preferably, the methylhydrosiloxane-dimethylsiloxane copolymer is a low molecular weight type with a molecular weight of 1000-5000 g / mol.

[0037] Preferably, the organic solvent a includes xylene and / or trimethylbenzene, both of which are commercially available products.

[0038] More preferably, the raw materials of component A, by mass percentage, include: 17% methylphenyl polysiloxane, 17% methylhydrosiloxane-dimethylsiloxane copolymer, 2% defoamer, 2% anti-settling agent, 10% organic solvent a, 3% silane coupling agent, and 17% pigment, and the balance being silanol-terminated polydimethylsiloxane.

[0039] In some preferred embodiments, the raw materials of component B, by mass percentage, include: 50-60% ethyl silicate (Evonik product model: TYZOR® TPT) and the balance organic solvent b.

[0040] Of which, based on the total mass of component B as 100%, the amount of ethyl silicate added is 50-60%, for example, it can be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, etc. Ethyl silicate, as the core crosslinking agent, reacts with silanol groups and is key to achieving paint film curing.

[0041] Preferably, the organic solvent b includes xylene and / or trimethylbenzene, both of which are commercially available products.

[0042] In some preferred embodiments, the raw materials of component B include, by mass percentage: 55% ethyl silicate and 45% organic solvent b.

[0043] A second aspect of the present invention provides a method for preparing a long-lasting biomimetic antimicrobial functional coating, comprising: mixing component A and component B to obtain the long-lasting biomimetic antimicrobial functional coating; Component A is prepared by mixing silanol-terminated polydimethylsiloxane, methylphenyl polysiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, additives and organic solvent a. Component B is prepared by mixing ethyl silicate and organic solvent b.

[0044] In some preferred embodiments, component A is prepared by the following steps: (a) Mix the anti-settling agent, defoamer and part of organic solvent a to form a matrix slurry; (b) Add pigment to the matrix slurry to obtain a color paste; (c) Grinding the pigment paste; (d) The ground color paste, silanol-terminated polydimethylsiloxane and methylphenyl polysiloxane are mixed, and then methylhydrosiloxane-dimethylsiloxane copolymer and silane coupling agent are added to obtain component A; Preferably, the stirring time in step (a) is 10-15 minutes, for example, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, etc.; Preferably, the stirring time in step (b) is 30-45 minutes, for example, 30 minutes, 35 minutes, 40 minutes, 45 minutes, etc.; Preferably, in step (c), the fineness of the pigment paste after the grinding process is ≤25μ; Preferably, in the preparation of component A, after the main resin mixing is completed, the process further includes: cleaning the production equipment with the reserved organic solvent a, reusing the cleaning solution, adjusting the viscosity as needed, and finally obtaining component A; Preferably, component B is prepared by the following steps: mixing ethyl silicate and organic solvent b, and then filtering through an 80-120 mesh filter to obtain component B.

[0045] In a preferred embodiment of the present invention, the preparation method of the long-lasting biomimetic antimicrobial functional coating includes: preparing a sample according to the following steps: 1. Preparation of component A: (1) Add some xylene, anti-settling agent and defoamer to the mixing tank under low speed stirring.

[0046] (2) Stir at low speed for about 10-15 minutes to fully wet and disperse the anti-settling agent and form a uniform gel-like liquid.

[0047] (3) Add iron oxide red slowly to prevent dust from flying.

[0048] (4) After adding, increase the speed of the disperser to carry out high-speed dispersion. The recommended linear velocity of the disc edge is 20-25 m / s.

[0049] (5) The high-speed dispersion time is about 30-45 minutes until the slurry looks uniform and there are no obvious dry powder particles.

[0050] (6) Grind the dispersed slurry using a sand mill.

[0051] (7) Grind to a fineness of ≤25μ. The grinding process provides stronger shear force, which can completely open up pigment aggregates and ensure color performance and coating gloss.

[0052] (8) Transfer the ground color paste to the paint mixing tank, and slowly add silanol-terminated polydimethylsiloxane and methylphenyl polysiloxane while stirring at low speed.

[0053] (9) Stir at low speed for about 20 minutes to ensure that it is fully mixed.

[0054] (10) Under low-speed stirring, slowly add methylhydrosiloxane-dimethylsiloxane copolymer and silane coupling agent. This component can be used as an auxiliary crosslinking agent to enhance the crosslinking density and performance of the coating film.

[0055] (11) Clean the grinder and container with the remaining xylene and add all the cleaning solution into the paint mixing tank.

[0056] (12) Stir at high speed for at least 30 minutes to ensure that the entire system is completely homogeneous.

[0057] (13) Use a filter screen with an appropriate mesh size to filter the coating and remove any impurities or small amounts of gel particles that may be present.

[0058] (14) Put the filtered paint into a clean, dry, and sealed container.

[0059] 2. Preparation of component B: (1) Add xylene to a clean, dry, and moisture-free reaction vessel.

[0060] (2) Add ethyl silicate while stirring slowly.

[0061] (3) Stir at medium speed for 15 minutes to ensure that all components are fully mixed and form a homogeneous and transparent solution.

[0062] (4) After passing the inspection, the coating should be filtered through an 80-120 mesh filter and packaged. It must be sealed and stored to prevent the coating from curing after contact with moisture in the air.

[0063] The third aspect of the present invention provides a long-lasting biomimetic antimicrobial functional coating or the application of a long-lasting biomimetic antimicrobial functional coating prepared by the aforementioned preparation method in the preparation of a long-lasting biomimetic antimicrobial functional coating.

[0064] The long-lasting biomimetic antimicrobial functional coating provided by this invention differs from traditional antifouling paints, which "poison" marine organisms by continuously releasing biocides such as copper. This coating relies on its extremely low surface energy (physical action) and releases absolutely no toxic substances. It fully complies with and even exceeds environmental restrictions on antifouling paints worldwide. Simultaneously, the coating surface is extremely smooth and elastic, maintaining minimal frictional resistance at all times. Fouling organisms do not adhere firmly and are easily removed by water flow, thus maintaining a clean hull for a long time and reducing fuel consumption by up to 10-15%.

[0065] The present invention will be further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0066] The raw materials used in the following examples are: Silanol-terminated polydimethylsiloxane (Dow Chemical product model: DC-1107); Methylphenyl polysiloxane (Wacker Chemie AG product model: AK-50); Methylhydrosiloxane-dimethylsiloxane copolymer (Wacker Chemie AG product model: HC 1107); Defoamer (BYK CHEMICAL product model: BYK-052); Anti-settling agent (Zhejiang Fenghong product model: SD-2); Iron oxide red (Shanghai Yipin Pigment product model: 190); Silane coupling agent (Evonik Industries AG product model: DYNASYLAN-DAMO); Ethyl silicate (Evonik product model: TYZOR® TPT).

[0067] Example 1 This embodiment provides a long-lasting biomimetic antimicrobial functional coating, comprising component A and component B; The raw materials for component A, by mass percentage, include: 20% methylphenyl polysiloxane; 17% methylhydrosiloxane-dimethylsiloxane copolymer; 2% defoamer; 1% antisettling agent; 20% iron oxide red; 10% xylene; 4% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0068] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0069] The preparation process of the long-lasting biomimetic antimicrobial functional coating is as follows: 1. Preparation of component A: (1) Add some xylene, anti-settling agent and defoamer to the mixing tank under low speed (300~350 rpm) stirring.

[0070] (2) Stir at low speed (300~350 rpm) for about 10-15 minutes to fully wet and disperse the anti-settling agent and form a uniform gel-like liquid.

[0071] (3) Add iron oxide red slowly to prevent dust from flying.

[0072] (4) After adding, increase the speed of the disperser to carry out high-speed dispersion, with the edge linear velocity of the disc at 25 m / s.

[0073] (5) The high-speed dispersion time is about 40 minutes until the slurry looks uniform and there are no obvious dry powder particles.

[0074] (6) Grind the dispersed slurry using a sand mill.

[0075] (7) Grind until the fineness reaches ≤25μ.

[0076] (8) Transfer the ground pigment to the paint mixing tank, and slowly add silanol-terminated polydimethylsiloxane and methylphenyl polysiloxane while stirring at low speed (300~350 rpm).

[0077] (9) Stir at low speed for about 20 minutes to ensure that it is fully mixed.

[0078] (10) Add methylhydrosiloxane-dimethylsiloxane copolymer and silane coupling agent slowly while stirring at low speed (300~350 rpm).

[0079] (11) Clean the grinder and container with the remaining xylene and add all the cleaning solution into the paint mixing tank.

[0080] (12) Stir at low speed (300~350 rpm) for at least 30 minutes to ensure that the whole system is completely homogeneous.

[0081] (13) Use an 80-120 mesh filter to filter the coating to remove any impurities or small amounts of gel particles that may be present.

[0082] (14) Put the filtered paint into a clean, dry, and sealed container.

[0083] 2. Preparation of component B: (1) Add xylene to a clean, dry, and moisture-free reaction vessel.

[0084] (2) Add ethyl silicate while stirring slowly.

[0085] (3) Stir at medium speed (500~550 rpm) for 15 minutes to ensure that all components are fully mixed and form a homogeneous and transparent solution.

[0086] (4) After passing the inspection, filter the product through an 80-120 mesh filter, package it, and seal it for storage.

[0087] 3. Component A and Component B are kept separate during storage and transportation. When used, they are mixed evenly at a volume ratio of Component A: Component B = 8:1 to obtain the long-lasting biomimetic antimicrobial functional coating.

[0088] Example 2 This embodiment provides a long-lasting biomimetic antimicrobial functional coating, comprising component A and component B; The raw materials for component A, by mass percentage, include: 17% methylphenyl polysiloxane; 17% methylhydrosiloxane-dimethylsiloxane copolymer; 2% defoamer; 2% antisettling agent; 17% iron oxide red; 10% xylene; 3% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0089] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0090] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 1.

[0091] Example 3 This embodiment provides a long-lasting biomimetic antimicrobial functional coating, comprising component A and component B; The raw materials for component A, by mass percentage, include: 14% methylphenyl polysiloxane; 20% methylhydrosiloxane-dimethylsiloxane copolymer; 1% defoamer; 3% anti-settling agent; 14% iron oxide red; 8% xylene; 2% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0092] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0093] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 1.

[0094] Example 4 This embodiment provides a long-lasting biomimetic antimicrobial functional coating, comprising component A and component B; The raw materials for component A, by mass percentage, include: 17% methylphenyl polysiloxane; 14% methylhydrosiloxane-dimethylsiloxane copolymer; 3% defoamer; 2% antisettling agent; 17% iron oxide red; 12% xylene; 3% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0095] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0096] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 1.

[0097] Application Examples 1-4 This application example provides a long-lasting biomimetic antimicrobial functional coating. Application examples 1-4 respectively use the long-lasting biomimetic antimicrobial functional coatings from Examples 1-4. The preparation process of the long-lasting biomimetic antimicrobial functional coating is as follows: (1) After cleaning the steel plate surface with solvent, use a sandblasting machine to thoroughly remove rust and achieve the Sa2.5 standard; (2) Apply general-purpose epoxy anti-rust paint by airless high-pressure spraying (dry film thickness between 150-220u), and wait for the paint film to cure and dry; (3) Apply airless high-pressure spray coating to the bonding paint (dry film thickness between 75-100u), and wait for the paint film to cure and dry; (4) Mix components A and B of the long-lasting biomimetic antimicrobial functional coating evenly at a volume ratio of 8:1; (5) Apply long-lasting biomimetic antimicrobial functional coating by airless high-pressure spraying, and wait for the coating film to cure and dry to obtain a long-lasting biomimetic antimicrobial functional coating (the dry film thickness of the coating is between 120 and 150 μm).

[0098] Comparative Example 1 This comparative example provides an antifouling coating, the raw materials of which include, by weight percentage: 32% acrylic silicone resin; 20% cuprous oxide; 10% bromopyrronitrile; 5% iron oxide red; 14% precipitated barium sulfate; 5% polyamide wax paste; 2% bentonite; and 12% xylene.

[0099] The acrylic silicone resin is selected from NITTO KASEI DO., LTD., Japan. The brominated pyrronitrile is selected from Wuxi Yaodexin Chemical, and the cuprous oxide is selected from Zhejiang Lijing. The precipitated barium sulfate is selected from Zhejiang Yong'an Weidun, and the iron oxide red is selected from Shanghai Yipin, while the bentonite is selected from Zhejiang Fenghong. The polyamide wax paste is selected from Kusunoki Chemical, Japan.

[0100] The preparation process of the antifouling coating is as follows: 1) Add 1 / 3 of the acrylic silicone resin and 1 / 3 of the xylene to a clean mixing tank and stir well.

[0101] 2) Add bentonite at a slow speed (300-350 rpm) and then at a high speed (800 rpm) for 20 minutes until the bentonite forms a gel.

[0102] 3) Add 1 / 3 of the acrylic silicone resin, copper oxide, bromopyronitrile, iron oxide red and precipitated barium sulfate at a slow speed (300-350 rpm) and at a high speed (800 rpm) for 30 minutes until the fineness is ≤50u.

[0103] 4) Add the polyamide wax paste at a slow speed (300-350 rpm) and stir at a high speed (800 rpm) until homogeneous.

[0104] 5) Add the remaining acrylic silicone resin and xylene at a slow speed (300-350 rpm) and stir at a medium speed (500-550 rpm) until homogeneous.

[0105] 6) Filter and package using an 80-120 mesh filter: Comparative Example 2 This comparative example provides a coating that differs from Example 2 in that component A does not contain methylphenyl polysiloxane.

[0106] The raw materials for component A, by mass percentage, include: Methylphenyl polysiloxane 0%; methylhydrosiloxane-dimethylsiloxane copolymer 17%; defoamer 2%; anti-settling agent 2%; iron oxide red 17%; xylene 10%; silane coupling agent 3%; balance silanol-terminated polydimethylsiloxane.

[0107] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0108] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 1.

[0109] Comparative Example 3 This comparative example provides a coating that differs from Example 2 in that component A does not contain methylhydrosiloxane-dimethylsiloxane copolymer.

[0110] The raw materials for component A, by mass percentage, include: 17% methylphenyl polysiloxane; 0% methylhydrosiloxane-dimethylsiloxane copolymer; 2% defoamer; 2% antisettling agent; 17% iron oxide red; 10% xylene; 3% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0111] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0112] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 1.

[0113] Comparative Application Examples 1-3 This comparative application example provides an antimicrobial functional coating, which differs from application example 1 in that comparative application examples 1-3 respectively use the coatings in comparative examples 1-3.

[0114] Comparative Application Example 4 This comparative example provides an antimicrobial functional coating, which differs from application example 2 in that the ratio of component A to component B is 7:1.

[0115] The raw materials for component A, by mass percentage, include: 17% methylphenyl polysiloxane; 17% methylhydrosiloxane-dimethylsiloxane copolymer; 2% defoamer; 2% antisettling agent; 17% iron oxide red; 10% xylene; 3% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0116] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0117] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 2.

[0118] Comparative Application Example 5 This comparative example provides an antimicrobial functional coating, which differs from application example 2 in that the ratio of component A to component B is 9:1.

[0119] The raw materials for component A, by mass percentage, include: 17% methylphenyl polysiloxane; 17% methylhydrosiloxane-dimethylsiloxane copolymer; 2% defoamer; 2% antisettling agent; 17% iron oxide red; 10% xylene; 3% silane coupling agent; the balance being silanol-terminated polydimethylsiloxane.

[0120] The raw materials of component B, by mass percentage, include: 55% ethyl silicate and 45% xylene.

[0121] The preparation process of the long-lasting biomimetic antimicrobial functional coating is the same as in Example 2.

[0122] The coated samples prepared using Application Examples 1-4 were used for testing; The coated samples prepared in Comparative Application Examples 1-5 were used for testing.

[0123] Test method: Shallow sea immersion test was conducted in accordance with GB / T 6822-2024 standard for antifouling and antirust paint system for ship hulls (tested at Xiamen 725 Institute).

[0124] The test results are shown in Table 1.

[0125] Table 1. Performance data of coatings

[0126] The comparative tests above show that the long-lasting biomimetic antimicrobial coating provided by the present invention has significant advantages over conventional antifouling coatings in all test indicators. In particular, the coating of Example 2 of the present invention has excellent performance in terms of product stability, the appearance of the painted surface after coating, and the effect of preventing marine organisms from attaching, which can meet the needs of ship navigation.

[0127] In summary, compared with existing technologies, the long-lasting biomimetic antimicrobial coating and method for antifouling substrate surfaces provided by this invention produce a non-toxic or extremely low-toxic coating film. Its core feature is the creation of an extremely smooth, low-surface-energy surface. While marine organism spores or larvae can temporarily attach, their adhesion is very weak. When a ship reaches a certain speed, the shear force generated by the water flow easily peels off the biofouling. This coating solves the problem of existing self-polishing antifouling coatings emitting large amounts of volatile organic compounds (VOCs) that pollute the environment. It avoids the VOC emission problems associated with antifouling coatings.

[0128] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A long-acting biomimetic antimicrobial functional coating, characterized by, The A component and the B component are mixed to obtain the long-acting biomimetic antimicrobial functional coating. The A component includes the following raw materials: silanol-terminated polydimethylsiloxane, methylphenylpolysiloxane, methylhydrogen polysiloxane-dimethylsiloxane copolymer, additives, and organic solvent a; The B component includes the following raw materials: ethyl silicate and organic solvent b.

2. The long-acting biomimetic antimicrobial functional coating according to claim 1, characterized in that, The volume ratio of the A component and the B component is 7-9:

1.

3. The long-acting biomimetic antimicrobial functional coating according to claim 1, characterized in that, The additives include defoaming agent, anti-settling agent, pigment, and silane coupling agent.

4. The long-acting biogenic antimicrobial functional coating according to claim 3, characterized in that, The raw materials of the A component include, in mass percentage: methylphenylpolysiloxane 14%-20%, methylhydrogen polysiloxane-dimethylsiloxane copolymer 14%-20%, defoaming agent 1%-3%, anti-settling agent 1%-3%, organic solvent a 8%-12%, silane coupling agent 2%-4%, and pigment 14%-20%, and the rest is silanol-terminated polydimethylsiloxane; Preferably, the viscosity of the silanol-terminated polydimethylsiloxane is 1000-20000 mPa.s; Preferably, the molecular weight of the methylhydrogen polysiloxane-dimethylsiloxane copolymer is 1000-5000 g / mol; Preferably, the organic solvent a includes xylene and / or trimethylbenzene; Preferably, the pigment includes one or more of iron oxide red, large red powder, phthalocyanine blue, and phthalocyanine green.

5. The long-acting biogenic antimicrobial functional coating according to claim 1, characterized in that, The raw materials of the A component include, in mass percentage: methylphenylpolysiloxane 17%, methylhydrogen polysiloxane-dimethylsiloxane copolymer 17%, defoaming agent 2%, anti-settling agent 2%, organic solvent a 10%, silane coupling agent 3%, and pigment 17%, and the rest is silanol-terminated polydimethylsiloxane.

6. The long-acting biomimetic antimicrobial functional coating of claim 1, wherein, The raw materials of the B component include, in mass percentage: ethyl silicate 50%-60% and the rest is organic solvent b; Preferably, the organic solvent b includes xylene and / or trimethylbenzene.

7. The long-acting biomimetic antimicrobial functional coating according to claim 1, wherein, The raw materials of the B component include, in mass percentage: ethyl silicate 55% and organic solvent b 45%.

8. The method for preparing a long-acting biomimetic antimicrobial functional coating according to any one of claims 1 to 7, characterized in that, The A component and the B component are mixed to obtain the long-acting biomimetic antimicrobial functional coating. The A component is prepared by mixing silanol-terminated polydimethylsiloxane, methylphenylpolysiloxane, methylhydrogen polysiloxane-dimethylsiloxane copolymer, additives, and organic solvent a; The B component is prepared by mixing ethyl silicate and organic solvent b. The A component is prepared by the following steps:

9. The preparation method according to claim 8, characterized in that, (a) mixing anti-settling agent, defoaming agent, and part of organic solvent a to form a base slurry; (b) adding pigment to the base slurry to obtain a color slurry; (c) performing grinding treatment on the color slurry; (d) mixing the ground color slurry, silanol-terminated polydimethylsiloxane, and methylphenylpolysiloxane, and then adding methylhydrogen polysiloxane-dimethylsiloxane copolymer and silane coupling agent to obtain the A component; Preferably, the stirring time in step (a) is 10-15 minutes; Preferably, the stirring time in step (b) is 30-45 minutes; Preferably, in step (c), the fineness of the color slurry after the grinding treatment is ≤25 μ. ​ Preferably, in the preparation of the A component, after the completion of the main resin mixing, it further comprises: cleaning the production equipment with the reserved organic solvent a, and recycling the cleaning liquid, and adjusting the viscosity as needed, to finally obtain the A component; Preferably, the B component is prepared by mixing ethyl silicate and organic solvent b, and then filtering through an 80-120 mesh filter to obtain the B component.

10. Use of the long-acting biomimetic antimicrobial functional coating according to any one of claims 1-7 or prepared by the preparation method according to claim 8 or 9 in the preparation of a long-acting biomimetic antimicrobial functional coating.

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