Environment-friendly and efficient surface fish-skin-imitated protective material, construction method and product thereof

Abstract

The invention relates to the technical field of ship antifouling materials and environmental protection, and discloses an environment-friendly and efficient surface fish-skin-imitated protective material, a construction method and a product. The environment-friendly and efficient surface fish-skin-imitated protective material is prefabricated in a factory and comprises a release layer and a coiled material of an elastic low-surface-energy fish-skin-imitated coating protective film layer; the elastic low-surface-energy fish-skin-imitating coating protective film layer is formed by coating a release layer with a low-surface-energy fish-skin-imitating coating in advance and drying the coating, and then winding the coating and the release layer together to form a coiled material which is continuous in the length direction. By means of material structure simplification and collaborative improvement of a formula and a construction process, the effects of saving labor, labor and materials, being high in efficiency, environmentally friendly, long in service life and the like are achieved, the cost of multiple links such as material manufacturing, transportation and construction is greatly reduced, and the requirements of industries such as manufacturing and maintenance of ships and other marine traffic tools, equipment and facilities can be met.

Description

Technical Field

[0001] This invention relates to the field of antifouling materials and environmental protection technology, specifically to an environmentally friendly and efficient fish-skin-like protective material for ship surfaces, its preparation method, and its products, which are particularly suitable for antifouling protection of various types of ships. Background Technology

[0002] The attachment and accumulation of microorganisms and marine flora and fauna on the surfaces of ship hulls or other water transport equipment and facilities increases the weight and roughness of the hull, leading to increased energy consumption and greenhouse gas emissions, thus increasing the burden on the marine environment, ecological security, and economy. In particular, with the International Maritime Organization (IMO) continuously raising environmental protection requirements and increasing pressure on ship operating costs, the development of environmentally friendly and efficient fish-skin-like surface protective materials and construction methods has become increasingly urgent.

[0003] For example, existing technologies typically involve spraying low surface energy antifouling paint onto the hull shell on-site. Because low surface energy antifouling paint has low adhesion strength, a primer and a bonding coat must first be prepared on the hull shell. For instance, the low surface energy antifouling paint application method for the outer hull plating provided in CN112221905 A requires first applying an 80-300 micrometer anti-rust primer to the bottom section on-site, then applying a 50-120 micrometer bonding coat, and finally applying a 50-120 micrometer self-polishing antifouling paint. Therefore, the process is complex, involves multiple layers of paint spraying on-site, and is labor-intensive, material-intensive, time-consuming, and environmentally unfriendly. The underwater coating application method for shipbuilding disclosed in CN112024340 A also requires on-site mixing of underwater coatings and coating application treatment, which includes undercoat treatment, intermediate coat treatment, and topcoat treatment.

[0004] Currently, some literature also uses repair tape to obtain small-area silicone low-friction antifouling adhesive films. These films have a three-layer structure: a bottom adhesive layer, a plastic base film layer, and a silicone low-friction antifouling layer. In use, the bottom adhesive layer is bonded to the outer surface of the ship, exposing the silicone low-friction antifouling layer to achieve antifouling. However, firstly, this adhesive film is small in scale during actual manufacturing and is mainly used for repair work, requiring consideration of construction and rework, resulting in a small actual antifouling area. Secondly, it must be combined with a first release film and a second release film for actual manufacturing and use, resulting in a five-layer structure including the first and second release films, making the manufacturing process complex and costly. Thirdly, the plastic base film layer is prone to aging, hardening, and brittleness in outdoor environments, limiting its actual lifespan and easily causing the antifouling adhesive film to detach in sheets. Fourthly, its static antifouling ability is poor; even when the ship is moored for a long time (or other fixed water equipment and facilities), it still cannot effectively prevent the attachment and accumulation of microorganisms and marine flora and fauna on the surface. CN 118421211 A provides an adhesive low surface energy organic fluorine antifouling flexible film and its preparation method. The antifouling flexible film contains adhesive and has great adhesiveness. In practice, the prepared modified organic fluorine antifouling flexible film needs to be coated with an organic film for protection using a two-roll mill. It has a three-layer structure. In practical applications, it has been found that the adhesiveness leads to a significant decrease in its antifouling effect and it is easy to be damaged during construction.

[0005] In summary, existing antifouling materials and construction technologies for ship surfaces (especially below the waterline) mainly involve on-site spraying and multi-coat application, or the application of multi-layer antifouling adhesive films with plastic substrates onto the outer surface of the ship. These methods suffer from problems such as complex material structures, high labor and material costs, complex manufacturing processes and high costs, low efficiency, environmental unfriendliness, short lifespan, and difficulty in achieving both adhesion and antifouling performance, as well as dynamic and static antifouling capabilities. Consequently, they fail to meet the needs of the manufacturing and maintenance industries for ships and other waterborne equipment and facilities. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention aims to provide an environmentally friendly and efficient surface-imitating fish skin protective material, construction method, and product. Through the synergistic improvement of material structure simplification and coating formulation and construction process, the material performance and structure are suitable for mass prefabrication in factories, and a balance is achieved between adhesion and antifouling performance, dynamic antifouling and static antifouling. This results in significant simplification of material structure, preparation, and construction process, saving labor, materials, and achieving high efficiency, environmental friendliness, and long service life, thus meeting the needs of the manufacturing and maintenance industries of ships and other waterborne equipment and facilities.

[0007] To achieve the above objectives, the present invention provides the following technical solution: An environmentally friendly and efficient surface-imitating fish skin protective material is prefabricated in a factory. It comprises a release layer and an elastic low-surface-energy fish skin-imitating coating protective film. The elastic low-surface-energy fish skin-imitating coating protective film is formed by pre-coating and drying the low-surface-energy fish skin-imitating coating onto the release layer, and then winding it together with the release layer to form a continuous roll in the length direction. The average thickness of the elastic low-surface-energy fish skin-imitating coating protective film is 100~300 µm, and the elastic modulus E is 0.5 MPa≤E≤2.5 MPa. It is formed by directly coating the low-surface-energy fish skin-imitating coating onto the release surface of the release layer and then drying it. The width of the roll ranges from 0.2 to 2 m, and the length of a single roll can be prepared according to engineering needs, typically 300-1000 m.

[0008] The release layer is a double-sided release film, with one side of the film being a light release surface and the other side being a heavy release surface. The low surface energy fish skin-like coating is pre-coated on the heavy release surface and dried. After winding, the outer side of the elastic low surface energy fish skin-like coating protective film layer contacts the light release surface, forming a roll with different release forces on both sides of the elastic low surface energy fish skin-like coating protective film layer.

[0009] A method for preparing the aforementioned environmentally friendly and efficient fish-skin-like protective material includes the following steps: B1. Pre-preparation of elastic low surface energy fish skin-like coating and double-sided release film; B2. On the production line, the double-sided release film roll is continuously unfolded and laid flat, with the heavy release side facing upwards; B3. Apply the elastic low surface energy fish skin-like coating evenly to the release surface and let it dry. If the coating film thickness obtained by a single coating is less than 100~300 µm, apply a second or multiple coatings. B4. After drying, the coating film is bonded to the release surface to form an elastic, low surface energy fish skin-like protective coating film. The double-sided release film forms a release layer. Finally, the elastic, low surface energy fish skin-like protective coating film and the release layer are concentrically wound to obtain a roll of environmentally friendly and efficient fish skin-like protective material for ship surfaces.

[0010] An environmentally friendly and efficient surface imitation fish skin protective construction method, which uses the aforementioned roll-type environmentally friendly and efficient surface imitation fish skin protective material, includes the following steps: C1. Pre-treat the outer surface of the ship or water equipment, including grinding it smooth, removing oil, rust and impurities, and letting it dry. C2. The pre-prepared adhesive is uniformly applied to the outer surface of the ship to form a ship surface bonding layer. The adhesive is used to bond the outer surface of the elastic low surface energy imitation fish skin coating protective film to the outer surface of the ship, and to make the bonding strength between the outer surface of the protective film and the outer surface of the ship greater than the bonding strength between the inner surface of the protective film and the release surface. C3. During the initial curing period after applying the bonding adhesive, the outer surface of the protective film layer of the roll of environmentally friendly and efficient imitation fish skin protective material for ship surfaces is turned towards the ship surface bonding layer. The film layer is then gradually unfolded and pressure is applied from the side of the light release surface to ensure that the protective film layer is tightly attached to the ship surface bonding layer. C4. When the bonding strength between the protective film layer and the ship surface bonding layer is greater than the bonding strength between the inner surface of the protective film layer and the release surface, the release layer is peeled off one by one from the outside along the direction parallel to the plane extending from the ship surface, so that the inner surface of the protective film layer is exposed to the outside, forming a low surface energy imitation fish skin coating protective surface bonded to the ship surface. C5. The adhesive continues to cure at room temperature until it is fully cured, firmly bonding the protective film to the outer surface of the ship. It provides antifouling protection during navigation and when the ship is at rest, and reduces the friction between the outer surface of the ship and the water below the waterline during navigation.

[0011] An environmentally friendly and efficient surface imitation fish skin protective product is a product obtained by using the aforementioned surface imitation fish skin protective material or by using the aforementioned surface imitation fish skin protective construction method; the product is a product in which the inner surface of the protective film layer is exposed to the outside after the release layer is peeled off, and a low surface energy imitation fish skin coating protective surface is formed on the outer surface of the product; the product includes ships or underwater navigation water vehicles that require surface antifouling treatment, as well as water equipment and facilities.

[0012] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention breaks through the limitations of existing similar materials and construction processes by simplifying the material structure and synergistically improving the coating formulation and construction process. It makes the material performance and structure more suitable for mass prefabrication in factories and achieves a balance between adhesion and antifouling performance, dynamic antifouling and static antifouling. It achieves a significant simplification of material structure and preparation and construction process, saving labor, effort, and materials, and has the effects of high efficiency, green environmental protection and long service life. It greatly reduces the cost of multiple links such as material manufacturing, transportation and construction, and can meet the needs of the manufacturing and maintenance of ships and other water transportation vehicles, equipment and facilities.

[0013] (2) The environmentally friendly and efficient fish-skin-like protective material provided by this invention is a prefabricated roll material in a factory, consisting of only a release layer and an elastic low-surface-energy fish-skin-like coating protective film. The elastic low-surface-energy fish-skin-like coating protective film is pre-coated onto the release layer and dried on the factory production line, and then wound together with the release layer to form a continuous roll material in the length direction. The two sides of the protective film layer are isolated by the two sides of the release layer in the rolled material, which facilitates manufacturing, transportation and use. The surface bonding strength of the protective film layer is low. Based on the bottom surface characteristics of organosilicon, the protective film layer has virtually no adhesive force. On the one hand, it can fix the protective film layer on the release layer and can be easily peeled off after construction. On the other hand, its low surface energy can maintain a high anti-fouling effect, achieving a diversified balance between material and construction, adhesion and anti-fouling performance, and dynamic and static anti-fouling requirements.

[0014] (3) The method for preparing environmentally friendly and efficient surface imitation fish skin protective material provided by the present invention is suitable for mass production on the production line of the factory. It can ensure stable product quality and is easy to manufacture, package, transport, store and use. Its width and length can be set as needed. It can be widely used in the manufacture and maintenance of ships and other transportation vehicles, as well as the manufacture or maintenance of other water equipment and facilities. It is green and environmentally friendly, and the utilization rate of coatings and other materials is high, which greatly reduces the overall cost.

[0015] (4) The environmentally friendly and efficient surface imitation fish skin protection construction method provided by the present invention uses factory-prefabricated rolls of environmentally friendly and efficient surface imitation fish skin protection material. On-site, only conventional primer and adhesive coating are required on the product surface. The roll material is directly attached to the outer surface of the product within multiple process windows, and the release layer is simply peeled off to complete the construction. Then, wait for the adhesive to fully cure. The construction is fast, efficient and short, thus avoiding the time-consuming, material-intensive, polluting and expensive on-site coating process of antifouling coatings. It also completely avoids the problems of unstable antifouling layer thickness and surface roughness obtained during on-site construction.

[0016] (5) The environmentally friendly and efficient surface imitation fish skin protective products provided by the present invention include ships or underwater navigation water vehicles that require surface antifouling treatment, as well as water equipment and facilities. They have greatly broken through the limitations of existing similar materials and construction processes, and their construction methods are more efficient and flexible. When carrying out emergency repair and maintenance operations, in conjunction with underwater curing adhesive, glass fiber cloth base film and other materials, a technical solution for direct underwater construction is also provided, which does not require entering the dock or other special repair facilities. This can greatly improve the efficiency of repair and maintenance operations and reduce the overall cost of multiple links. Detailed Implementation

[0017] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0018] In the following examples and comparative examples, except for the specially specified modified perfluoropolyether and other self-made materials, all other compounds and related reagents used can be purchased from the market. Among them, the CAS number of the hydroxyl-terminated polydimethylsiloxane is 70131-67-8; the silica is of type A200 and was purchased from Shandong Wanhua Tianhe New Materials Co., Ltd.; the particle size of the nano cuprous oxide is 30-50nm; and the number average molecular weight of the vinyl-terminated perfluoropolyether is 1000 and was purchased from Hubei Xinyuhong Biomedical Technology Co., Ltd.

[0019] Basic Implementation The environmentally friendly and efficient fish-skin-like protective material provided in this embodiment is a two-layer roll material prefabricated on a factory production line. It includes a release layer and an elastic low-surface-energy fish-skin-like coating protective film layer. The elastic low-surface-energy fish-skin-like coating protective film layer is formed by pre-coating the low-surface-energy fish-skin-like coating onto the release layer and drying it, and then winding it together with the release layer to form a continuous roll material in the length direction. In the winding state, the two sides of the release layer simultaneously separate the two sides of the protective film layer, preventing the inner and outer sides of the protective film layer from contacting each other.

[0020] The average thickness of the elastic low surface energy imitation fish skin coating protective film layer is 75~150 µm, and the elastic modulus E is 0.5 MPa≤E≤1.5 MPa. It is formed by directly coating the low surface energy imitation fish skin coating onto the release surface of the release layer and then drying it. The width of the roll material ranges from 0.2 to 2 m, and the length of a single roll is prepared according to the engineering needs, usually 300-1000 m.

[0021] The low surface energy fish skin-like coating is made of component A and component B; Component A, by weight, includes the following raw materials: 70-75 parts of hydroxyl-terminated polydimethylsiloxane, 15-25 parts of xylene, 2-4 parts of silicon dioxide, 2-5 parts of iron oxide, 0.5-1 parts of nano-cuprous oxide with a particle size of 30-50 nm, and 1-3 parts of cuprous thiocyanate. Component B, by weight, includes the following raw materials: 40-45 parts of trimethylsiloxytriethoxysilane, 10-12 parts of acetylacetone, 40-50 parts of xylene, 0.01-0.02 parts of organotin, and 1-3 parts of modified perfluoropolyether. The modified perfluoropolyether is prepared using the following steps: A1. Add 2,2-difluoro-2-iodo-1-acetophenone, benzaldehyde and indium powder to deionized water, react at 45-55℃ for 2-3 h, extract with ethyl acetate, combine the organic phases and dry with anhydrous sodium sulfate for 60-90 min, evaporate by rotary evaporation and elute by silica gel column chromatography to obtain α,α-difluoro-β-hydroxy ketone. A2. Add the α,α-difluoro-β-hydroxy ketone obtained in step A1 and acrylic acid to toluene, add a catalyst, react at 70-80℃ for 2-3 hours, and dry to obtain the compound; A3. Add the terminal vinyl perfluoropolyether, the compound obtained in step A2, KH-570 silane coupling agent, hexa(3-mercaptopropionic acid) dipentaerythritol ester and azobisisobutyronitrile to hexafluoroisopropanol, react at 50-60℃ for 2-4 hours, and rotary evaporate to obtain the modified perfluoropolyether.

[0022] The elastic, low surface energy, fish-skin-like protective coating layer is prepared using the following steps: S1. Add hydroxyl-terminated polydimethylsiloxane to a portion of xylene, stir at 20-30℃ for 20-30 min, add silica and stir at high speed for 30-60 min, then add iron oxide, nano cuprous oxide, cuprous thiocyanate and the remaining xylene, stir for 1-2 h to obtain component A. S2. Add trimethylsiloxytriethoxysilane to xylene and stir at 20-30℃ for 20-30 min. Add acetylacetone and organotin and continue stirring for 10-20 min. Finally, add modified perfluoropolyether and stir for 30-60 min to obtain component B. S3. Add component B obtained in step S2 to component A obtained in step S1, stir at 800-1000 rpm for 3-5 minutes, let stand for 3-5 minutes to obtain a low surface energy fish skin-like coating. S4. Apply the low surface energy imitation fish skin coating evenly to the release surface of the release layer. After curing and drying, an elastic low surface energy imitation fish skin coating protective film layer is obtained.

[0023] Low surface energy fish skin-like coatings can be prepared using various formulations and preparation methods, which will be explained in more detail in subsequent specific examples.

[0024] The release layer is a double-sided release film, with one side being a light release surface and the other side being a heavy release surface. The low surface energy fish skin-like coating is pre-coated on the heavy release surface and dried. After winding, the outer side of the elastic low surface energy fish skin-like coating protective film layer contacts the light release surface, forming a roll with different release forces on both sides (facilitating peeling in sequence). The double-sided release film can use various commercially available products, including but not limited to double-sided release films made of PET, PP, and PE materials, such as dual-silicone release film, PET / PP double-sided release film, PET double-sided release film, PE double-sided release film, PP double-sided release film, etc. The release forces on both sides and their differences can be selected according to actual needs.

[0025] A method for preparing an environmentally friendly and efficient surface-simulating fish skin protective material, used to prepare the aforementioned ship surface-simulating fish skin protective material, includes the following steps: B1. Pre-preparation of elastic low surface energy fish skin-like coating and double-sided release film; B2. On the production line, the double-sided release film roll is continuously unfolded and laid flat, with the heavy release side facing upwards; B3. Apply the elastic low surface energy fish skin-like coating evenly to the release surface and let it dry. If the coating film thickness obtained by a single coating is less than 75~150 µm, apply a second or multiple coatings. B4. After drying, the coating film is bonded to the release surface to form an elastic, low surface energy fish skin-like protective coating film. The double-sided release film forms a release layer. Finally, the elastic, low surface energy fish skin-like protective coating film and the release layer are concentrically wound to obtain a roll of environmentally friendly and efficient fish skin-like protective material for ship surfaces.

[0026] Steps B2 to B4 are carried out in a cleanroom, and the coating process in B3 is either scraping or roller coating.

[0027] An environmentally friendly and efficient surface imitation fish skin protective construction method, which uses the aforementioned roll-type environmentally friendly and efficient surface imitation fish skin protective material, includes the following steps: C1. Surface pretreatment: Pretreatment of the outer surface of the ship or other water equipment and facilities, including grinding the outer surface smooth, cleaning, rust removal, degreasing and other treatments, removing oil stains, rust and impurities, drying, so that the surface meets the Sa2.5 cleanliness requirements. C2. Applying bonding adhesive: Using a roller coating tool, uniformly apply the pre-prepared bonding adhesive to the treated outer surface to form a ship surface bonding layer with a thickness of 20-30 μm; this bonding adhesive is used to bond the outer surface of the elastic low surface energy imitation fish skin coating protective film to the outer surface of the ship, and to make the bonding strength between the outer surface of the protective film and the outer surface of the ship greater than the bonding strength between the inner surface of the protective film and the release surface; C3. Protective material application: After applying the bonding adhesive, usually within the initial curing time window (e.g., 20-30 minutes), the outer surface of the protective film layer of the roll of environmentally friendly and efficient imitation fish skin protective material for ship surfaces is gradually unfolded towards the ship surface bonding layer, and pressure is applied from the side of the light release surface to make the protective film layer tightly adhere to the ship surface bonding layer. C4. Release Layer Peeling: Allow the adhesive to continue curing at room temperature (e.g., 30-60 minutes) until the bond strength between the protective film and the ship surface bonding layer is greater than the bond strength between the inner surface of the protective film and the heavy release surface. Then, peel off the release layer gradually from the outside along the direction parallel to the plane extending from the ship surface, exposing the inner surface of the protective film to the outside, forming a low surface energy imitation fish skin coating protective surface bonded to the ship surface. C5. Curing and Molding: The adhesive continues to cure at room temperature (e.g., 6-12 hours) until fully cured, firmly bonding the protective film to the outer surface of the vessel, completing the construction. This protective film provides antifouling protection both during navigation and at rest, and reduces the friction between the vessel's outer surface and the water below the waterline during navigation.

[0028] The adhesive is one of a two-component epoxy resin adhesive, a two-component polyurethane adhesive, a moisture-curing silicone-modified polyurethane adhesive, a two-component acrylate adhesive, or a cyanoacrylate quick-drying adhesive, and may contain an alkyl coupling agent. The two-component epoxy resin adhesive is prepared from the following components in the following mass ratio: Component A: Liquid epoxy resin (E-51) 50-60 parts; n-Butanol 4-5 parts; Xylene 4-5 parts; Component B: Polyamide curing agent (650) 40-50 parts; Silane coupling agent (KH-560) 3-5 parts; Accelerator (DMP-30) 1-3 parts; Mixing ratio for use: A:B = 100:80-120; Specifically, the time window length for surface drying, initial curing, and complete curing can be adjusted by increasing or decreasing the parts of solvent, polyamide curing agent, and accelerator, respectively. Various formulations and preparation methods can be used, which will be described in detail in the following examples.

[0029] An environmentally friendly and efficient surface-imitating fish skin protective product is obtained by using the aforementioned surface-imitating fish skin protective material or by applying the aforementioned surface-imitating fish skin protective construction method. After peeling off the release layer, the inner surface of the protective film layer is exposed, forming a low surface energy fish skin-imitating coating protective surface on the outer surface of the product. The product includes ships or underwater navigation vehicles requiring surface antifouling treatment, as well as waterborne equipment and facilities. After construction, the adhesive cures naturally, firmly attaching the protective film layer to the outer surface of the product. Even in the event of external physical scratches or abrasions, it will not peel off in large pieces, but only locally at the site of the physical scratch or abrasion, making it easy to repair and restore quickly (if a plastic substrate is used, large pieces will peel off, making quick repair difficult).

[0030] The protective material provided by this invention adopts the form of prefabricated roll material, including a release layer and an elastic low surface energy imitation fish skin coating protective film layer. Through a combination of factory production and on-site construction, it achieves efficient antifouling protection for ship surfaces. The overall technical solution has the following characteristics: 1) It adopts the form of prefabricated roll material, which is convenient for factory production and on-site construction; 2) The imitation fish skin structure design, combined with low surface energy coating technology, achieves excellent antifouling effect; 3) The release layer design facilitates the unfolding and construction of the roll material; 4) Multiple bonding adhesive solutions are available to adapt to different construction needs; 5) It is an environmentally friendly material that meets the environmental protection requirements of the International Maritime Organization.

[0031] More specifically, five examples are described in detail below.

[0032] Example 1 The environmentally friendly and efficient surface-simulating fish skin protective material, construction method, and product provided in this embodiment are specific applications based on the previous embodiment. The difference lies in that it specifically addresses the problems of short lifespan and low batch construction efficiency of traditional antifouling materials, while also considering both dynamic and static antifouling needs. Its main application scenarios are new shipbuilding mass production lines and overall antifouling treatment for long-haul vessels. This material is a core antifouling silicone-based fish skin-simulating protective material, and the product is for newly built ships. The low surface energy fish skin-simulating coating is made of components A and B, the connecting adhesive is epoxy resin adhesive, and the construction process has been specifically selected. The release layer uses a PET double-sided release film, specifically including: The average thickness of the elastic low surface energy imitation fish skin coating protective film layer is 75~85 µm, and the elastic modulus E is 0.5 MPa≤E≤1.5 MPa. It is formed by directly coating the low surface energy imitation fish skin coating onto the release surface of the release layer and drying it. The roll width is 1.5~2m, and the single roll length is 100~1000m. The environmentally friendly organosilicon fish skin biomimetic coating used in this embodiment is composed of component A and component B. Component A, by weight, contains the following raw materials (total mass parts = 100): 72 parts of hydroxyl-terminated polydimethylsiloxane, 20 parts of xylene, 3 parts of silicon dioxide (A200), 3 parts of iron oxide, 0.7 parts of nano cuprous oxide, and 1.3 parts of cuprous thiocyanate. Component B, by weight, comprises the following raw materials (total parts by weight = 100): 42 parts of trimethylsiloxytriethoxysilane, 11 parts of acetylacetone, 44.985 parts of xylene, 0.015 parts of dibutyltin dilaurate, and 2 parts of modified perfluoropolyether-1. Release layer parameters: Select PET double-sided release film (substrate thickness 50μm), release force of 20g / in on the light release side, release force of 70g / in on the heavy release side, and release force difference of 50g / in (180° peel, 25℃); to match continuous and smooth peeling during mass production and mechanized mounting.

[0033] Protective film properties: average thickness 200μm, elastic modulus 1.2MPa, surface energy 21mN / m.

[0034] This embodiment describes a method for preparing an environmentally friendly silicone fish skin biomimetic coating and roll material, specifically designed to ensure stability in mass production. The method includes the following steps: Preparation of S1 and A components: Add hydroxyl-terminated polydimethylsiloxane to 10 parts (50% ratio) of xylene, stir at 25°C for 25 min, add silica and stir at 1500 rpm for 45 min, then add ferric oxide, nano cuprous oxide, cuprous thiocyanate and the remaining 10 parts (50% ratio) of xylene, and stir for 1.5 h. Preparation of components S2 and B: Trimethylsiloxytriethoxysilane was added to xylene and stirred at 25°C for 25 min. Acetylacetone and dibutyltin dilaurate were added and stirred for another 15 min. Finally, modified perfluoropolyether-1 was added and stirred for 45 min. S3. Coating mixing: Add component B obtained in step S2 to component A obtained in step S1. The mass ratio of component A to component B is 1:0.12. Stir at 900 rpm for 4 min and let stand for 4 min to obtain a low surface energy imitation fish skin coating. S4. Roll preparation: In a cleanroom, the PET release film is laid flat with the release side facing up. A roller coating process is used to coat the film with coating material (100μm at a time, applied in two coats to reach 200μm, and left to stand for 5 minutes). After drying, the film is concentrically wound to obtain a roll material with a length of 500m and a width of 1.8m per roll. S5. Further, the PET double-sided release film with elastic low surface energy imitation fish skin coating protective film layer is wound up. At this time, the light release film of the PET double-sided release film isolates the outer surface of the protective film layer, which can form a continuous length of roll material (usually 100~1000m). The width can be determined according to actual needs, one or more specifications. Generally, in shipbuilding, a wider roll material (e.g. 1~2m) is used, while a narrower roll material (e.g. 0.2~0.5m) is used for maintenance and repair. In actual use, the length and width of the roll material can be freely cut.

[0035] The specific components, proportions, and preparation method of modified perfluoropolyether-1 (specifically designed to improve antifouling properties and compatibility) are as follows: A1. 10 g of 2,2-difluoro-2-iodo-1-acetophenone, 4.2 g of benzaldehyde and 0.1 g of indium powder were added to 100 ml of deionized water and reacted at 50 °C for 2.5 h. Ethyl acetate was added for extraction, the organic phases were combined and dried over anhydrous sodium sulfate for 75 min. After rotary evaporation, silica gel column chromatography was used for elution and separation. The eluent was a mixture of petroleum ether and ethyl acetate in a mass ratio of 30:1 to obtain α,α-difluoro-β-hydroxy ketone. A2. Add 10g of the α,α-difluoro-β-hydroxy ketone obtained in step A1 and 3g of acrylic acid to 100ml of toluene, add 0.1g of 98wt% sulfuric acid, react at 75℃ for 2.5h, and dry to obtain the compound; A3. Add 17g of vinyl-terminated perfluoropolyether, 3g of the compound obtained in step A2, 2g of KH-570 silane coupling agent, 10g of dipentaerythritol hexa(3-mercaptopropionic acid) and 0.1g of azobisisobutyronitrile to 150ml of hexafluoroisopropanol, react at 55℃ for 3h, and rotary evaporate to obtain modified perfluoropolyether-1.

[0036] Increasing the content of modified perfluoropolyether (specifically including modified perfluoropolyether-1 to modified perfluoropolyether-5) in environmentally friendly silicone fish skin biomimetic coatings can correspondingly improve the oil resistance and solvent resistance of silicone coatings, and further enhance the coating's durability and other specific properties. It can be selected and used according to actual needs.

[0037] The adhesive used in this embodiment is a two-component epoxy resin adhesive. To adapt to batch construction and enhance bonding stability, it is made of the following components (parts by weight): 55 parts liquid epoxy resin (E-51), 45 parts polyamide curing agent (650), 4 parts silane coupling agent (KH-560), 9 parts n-butanol, 9 parts xylene, and 2 parts accelerator (DMP-30). Performance parameters: surface drying time 40 min, initial curing time 1.5 h, and complete curing time 7 h. In the above epoxy resin adhesive formulation, increasing the amount of solvent (n-butanol, xylene) will prolong the surface drying time after epoxy resin adhesive coating, and vice versa; increasing the amount of polyamide curing agent and / or accelerator will correspondingly shorten the initial curing time window and the complete curing time, and vice versa. The specific choice can be made according to the actual required construction time window.

[0038] In this embodiment, environmentally friendly and efficient surface imitation fish skin protective materials and construction methods are applied to newly manufactured ships. The specific construction process time window and material parameters can be reasonably selected according to the size of the ship.

[0039] The ship prepared according to the embodiments of the present invention has an elastic low surface energy fish skin-like protective film layer applied to its outer surface (especially the part below water). It has a fish skin biomimetic structure. The organosilicon segments and perfluoropolyether segments give the coating the characteristics of low surface energy and good flexibility. Copper ions can be slowly released from the coating to prevent microorganisms from forming biofilms and reduce the burden on the coating surface. The two work synergistically to exert a dual antifouling mechanism, which is environmentally friendly and reduces consumption. The introduction of modified perfluoropolyether can also improve the oil resistance and solvent resistance of the organosilicon coating, further improving the durability of the coating.

[0040] The environmentally friendly organosilicon fish skin biomimetic coating of this invention further enhances the dispersibility of perfluoropolyether in the organosilicon coating system by introducing hexa(3-mercaptopropionic acid) dipentaerythritol ester modified perfluoropolyether; mercapto active groups are introduced into the organosilicon coating system to achieve grafting of fluoroketone segments and KH-570 segments; due to the extremely low surface tension and migration ability of fluoroketone segments, they can quickly penetrate into the interface between stains and coatings, effectively wetting and loosening stains; the introduction of KH-570 segments improves the compatibility between modified perfluoropolyether and organosilicon coating, promotes the dispersion of modified perfluoropolyether in organosilicon polymers, and is conducive to further improving the detergency of organosilicon fish skin biomimetic coating.

[0041] The modified perfluoropolyether prepared in the embodiments of the present invention can form a cross-linked network structure in the organosilicon coating, which not only helps to improve the mechanical properties of the elastic low surface energy fish skin-like protective film, but also reduces the release rate of copper ions. At the same time, the sulfide structure in the modified perfluoropolyether can coordinate with copper ions, enabling the dynamic slow release of copper ions, achieving both dynamic and static antifouling, as well as long-term antifouling.

[0042] The embodiments of the present invention have the following characteristics: Balanced biomimetic coating formulation: The selection of A / B components and ratios in the environmentally friendly silicone fish skin biomimetic coating allows the antifouling agent and low surface energy components to work synergistically, achieving a balance between antifouling and adhesion; High-efficiency production: Factory-prefabricated rolls ensure uniform coating thickness and controllable quality; Smooth peeling: The PET release film has good stiffness and moderate release force differences, avoiding tangling, wrinkles, and peeling damage.

[0043] Through confidential testing, the environmentally friendly and highly efficient fish-skin-like protective material prepared by this invention is suitable for new shipbuilding production lines. Employing a mechanized continuous application process, the release film peeling efficiency reaches 30 m / h. Testing on the outer surface of a ship below the waterline showed that after 12 months of continuous marine immersion, barnacle adhesion area was <5% (antifouling grade 5), and adhesion reached JIS K5600 standard grade 3. Ship navigation resistance is reduced by more than 15%, antifouling life is extended to 4-5 years, and peeling efficiency is increased by 30% during batch construction, making it suitable for batch manufacturing of new ships and use on long-haul routes.

[0044] Example 2 The environmentally friendly and efficient surface imitation fish skin protective material, construction method and product provided in this embodiment are basically the same as those in Embodiment 1. The difference is that it is designed for the complex curved surfaces of old ships and provides an environmentally friendly water-based imitation fish skin protective material (low VOC), construction method and product.

[0045] 1. Environmentally friendly silicone fish skin biomimetic coating (low surface energy elastic fish skin coating) Component A (parts by mass, total = 100) consists of: 70 parts of hydroxyl-terminated polydimethylsiloxane, 25 parts of xylene, 2 parts of silicon dioxide, 2 parts of iron oxide, 0.5 parts of nano-cuprous oxide, and 0.5 parts of cuprous thiocyanate. Component B (parts by mass, total = 100) consists of: 40 parts of trimethylsiloxytriethoxysilane, 10 parts of acetylacetone, 48.99 parts of xylene, 0.01 parts of dibutyltin dilaurate, and 1 part of water-modified perfluoropolyether-2. 2. The preparation method of the environmentally friendly organosilicon fish skin biomimetic coating and roll material includes the following steps: Preparation of component A: Add 12.5 parts xylene to hydroxyl-terminated polydimethylsiloxane, stir at 20°C for 30 min, add silica and stir at 1500 rpm for 30 min, then add the remaining components and the remaining 12.5 parts xylene, and stir for 1 h; Preparation of component B: Trimethylsiloxytriethoxysilane was added to xylene and stirred at 20°C for 30 min. Acetylacetone and dibutyltin dilaurate were added and stirred for 10 min. Water-modified perfluoropolyether was slowly added and stirred for 30 min. Paint mixing: Mix components A and B at a mass ratio of 1:0.12, stir at 800 rpm for 5 minutes, and let stand for 5 minutes; Roll preparation: In a cleanroom, the PE release film is laid flat with the release side facing up, and the coating is applied (75μm in one coat, applied in two coats to reach 150μm). After drying at room temperature for 60 minutes, it is wound up. The length of a single roll is 300m and the width is 0.5m.

[0046] 3. Water-based modified perfluoropolyether-2 formulation (specifically improves water compatibility and environmental friendliness) The modified perfluoropolyether-2 used in this embodiment is based on the modified perfluoropolyether-1 formulation of Example 1, with the amount of acrylic acid added replaced by 4.5g, and the hexafluoroisopropanol in step A3 replaced by a mixed solvent of deionized water and ethanol (volume ratio 1:1). The reaction temperature was lowered to 50°C, and the drying time was extended to 2h to ensure water dispersibility.

[0047] 4. Adhesive formulation (suitable for manual application and bonding to curved surfaces) Components (parts by weight): 50 parts liquid epoxy resin (E-51), 50 parts polyamide curing agent (650), 3 parts silane coupling agent (KH-560), 10 parts n-butanol, 10 parts xylene, 3 parts accelerator (DMP-30); Main performance parameters: surface drying time 45 min, initial curing time 2 h, complete curing time 8 h, with better flexibility.

[0048] 5. Release film selection (matching curved surface bonding and manual peeling) Specific model: PE double-sided release film (substrate thickness 40μm); Release force parameters: 15g / in for light release surface, 55g / in for heavy release surface (180° peel, 25℃), with a release force difference of 40g / in; Protective film properties: average thickness 150μm, elastic modulus 0.7MPa, VOC content ≤28g / L.

[0049] This invention overcomes the problems of high VOC content and difficult construction on complex curved surfaces of old ships using traditional materials, making it suitable for scenarios with stringent environmental requirements. Testing shows its VOC content is ≤28g / L, meeting IMO Tier III environmental standards and causing no environmental pollution. The PE release film and water-based coating work synergistically to fit complex curved surfaces and corners of the hull. With an elastic modulus of 0.7MPa and excellent flexibility, it can tightly adhere to complex hull surfaces. Its low release force design ensures no residue after manual peeling, making it suitable for small-area repairs. After 9 months of immersion in the ocean, it achieves a level 4 antifouling rating (adhesion area <10%) and a level 2-3 adhesion rating, making it suitable for batch construction on old ship retrofits, inland waterway vessels, and port vessels with stringent environmental requirements.

[0050] Example 3 The environmentally friendly and efficient fish-skin-like protective material, construction method, and product provided in this embodiment are basically the same as those in Embodiments 1 and 2. The difference lies in that, to address the problems of easy damage and frequent maintenance of traditional materials, it achieves long-lasting antifouling and self-healing properties. Specifically, it provides a self-healing, long-lasting fish-skin-like protective material, suitable for antifouling treatment of ocean-going vessels and long-term moored water facilities (such as buoys and drilling platform auxiliary facilities). 1. Formulation of low-elasticity, low-surface-energy fish-skin-like coating Component A (parts by mass): 75 parts of hydroxyl-terminated polydimethylsiloxane, 15 parts of xylene, 4 parts of silicon dioxide (A200), 2 parts of iron oxide, 1 part of nano cuprous oxide, and 3 parts of cuprous thiocyanate; Component B (parts by weight): 45 parts trimethylsiloxytriethoxysilane, 11.8 parts acetylacetone, 40 parts xylene, 0.02 parts dibutyltin dilaurate, and 3 parts modified perfluoropolyether-3; Self-healing microcapsules comprising 5% of the total mass of components A and B.

[0051] 2. Modified perfluoropolyether-3 formulation (specifically improves long-lasting performance and cross-linking properties) Based on modified perfluoropolyether-1, the amount of acrylic acid added was increased to 4.5g, and the reaction time in step A3 was extended to 4h to enhance the crosslinking density and improve the toughness and self-healing foundation of the film.

[0052] 3. Adhesive formulation (suitable for long-lasting bonding and resistant to marine environmental corrosion) Components (parts by weight): 60 parts liquid epoxy resin (E-51), 40 parts polyamide curing agent (650), 5 parts silane coupling agent (KH-560), 8 parts n-butanol, 8 parts xylene, 1 part accelerator (DMP-30); Performance parameters: Surface drying time 30 min, initial curing time 2.5 h, complete curing time 8 h, bond strength increased by 15%.

[0053] 4. Self-healing microcapsule formula (added independently, accounting for 5% of the total mass of the imitation fish skin coating) Core material: 60 parts of silane repair agent (KH-550); Wall material: 40 parts of urea-formaldehyde resin; prepared by in-situ polymerization, with a particle size of 5-10 μm.

[0054] 5. Release membrane selection (matching long-term storage and microcapsule protection) Specific model: PET / PP composite double-sided release film (substrate thickness 60μm, PET layer + PP layer composite); Release force parameters: 25g / in for light release surface, 85g / in for heavy release surface (180° peel, 25℃), with a release force difference of 60g / in; 6. Preparation method of protective roll material (targeted protection microcapsules and improved long-term effectiveness) Preparation of component A: Add 7.5 parts xylene to hydroxyl-terminated polydimethylsiloxane, stir at 30°C for 20 min, add silica and stir at 1500 rpm for 60 min, then add the remaining components and the remaining 7.5 parts xylene, and stir for 2 h; Preparation of component B: Trimethylsiloxytriethoxysilane was added to xylene and stirred at 30°C for 20 min. Acetylacetone and dibutyltin dilaurate were added and stirred for 20 min. Modified perfluoropolyether-3 was added and stirred for 60 min. Coating mixing: Mix components A and B at a mass ratio of 1:0.12, stir at 1000 rpm for 3 minutes, let stand for 3 minutes, and then gently add the self-healing microcapsules at 500 rpm; Roll preparation: In a dust-free workshop, the PET / PP composite release film is laid flat with the release side facing up, coated with coating (80μm in one coat, 3 coats to 250μm), dried at low temperature (40℃) for 90min, and then wound up. The length of a single roll is 800m and the width is 2m.

[0055] 7. Precautions during construction Based on the aforementioned Examples 1 and 2, the bonding adhesive should be applied within 30 minutes to avoid the adhesive curing affecting the bonding; after application, let it stand for 1 hour before peeling off the release film, with slow and even movements and force controlled within 5N to avoid pulling the microcapsules; the construction environment temperature should be controlled at 15-30℃ and humidity ≤70% to avoid high temperature and high humidity affecting curing.

[0056] This invention addresses the problems of traditional antifouling materials being easily damaged and requiring frequent maintenance, achieving long-lasting antifouling and self-healing properties. It can be applied to antifouling treatment of ocean-going vessels and long-term moored water facilities (such as buoys and drilling platform auxiliary facilities). Its advantages include: self-healing function: the microcapsules release a repair agent after damage, achieving autonomous repair of scratches ≤0.8mm; long-lasting stability: the composite release film has strong impact resistance, protecting the microcapsules from rupture and providing a shelf life of up to 2 years; durable antifouling: the antifouling agent content reaches its maximum value, with high cross-linking density and a stable copper ion release rate.

[0057] Actual testing revealed the following protective membrane performance: elastic modulus 1.6 MPa, average thickness 250 μm, containing 5% self-healing microcapsules; antifouling and self-healing performance: service life in marine environments up to 6.5 years, copper ion slow release rate 0.05-0.1 μg / (cm²・d), self-healing rate ≥92% within 48 hours; cost reduction: impact resistance increased by 35%, frequency of damage repair reduced by 70%, and maintenance costs reduced by 60%.

[0058] Example 4 The environmentally friendly and efficient fish-skin-like protective material, construction method, and product provided in this embodiment are basically the same as those in Embodiments 1 to 3. The difference lies in that it addresses the problems of poor wear resistance and susceptibility to impact and scratch damage of traditional materials by improving the toughness and strength of the film layer, providing a graphene-based tough fish-skin-like protective material. It is primarily applied in scenarios such as high-speed ships, drilling platforms, and underwater equipment that are susceptible to impacts from marine floating bodies and scratches from fishing nets. Specifically: 1. Elastic, low surface energy fish skin-like coating formulation Component A (parts by mass): 73 parts hydroxyl-terminated polydimethylsiloxane, 18 parts xylene, 3 parts silica (A200), 4 parts iron oxide, 0.8 parts nano cuprous oxide (30-50nm), and 1.2 parts cuprous thiocyanate; Component B (parts by weight): 43 parts trimethylsiloxytriethoxysilane, 10.5 parts acetylacetone, 44.48 parts xylene, 0.02 parts dibutyltin dilaurate, and 2 parts modified perfluoropolyether-4; 2. Modified perfluoropolyether-4 formulation (specifically improves compatibility with graphene) Based on modified perfluoropolyether-1, the amount of vinyl-terminated perfluoropolyether added is increased to 22g, and 0.5g of graphene dispersant is added in step A3 to ensure synergistic dispersion with modified graphene oxide.

[0059] 3. Adhesive formulation (two-component acrylic adhesive, suitable for high-strength bonding and resistant to impact and scratches) Components (parts by weight): 55 parts epoxy acrylate resin (EA), 45 parts polyamide curing agent, 4 parts silane coupling agent (KH-570), 9 parts n-butanol, 9 parts xylene, 2 parts accelerator (DMP-30); Performance parameters: surface drying time 35 min, initial curing time 2 h, complete curing time 7 h, tensile bond strength ≥3.5 MPa.

[0060] 4. Modified graphene oxide (added independently, accounting for 5% of the total mass of the imitation fish skin coating) Graphene oxide was prepared using the Hummers method and modified with KH-570 to achieve a particle size of 1-5 μm, thereby improving its dispersibility and interfacial bonding in coatings.

[0061] 5. Release membrane selection (matching high-strength membrane layer and wear-resistant construction) Specific model: PP double-sided release film (substrate thickness 55μm) Release force parameters: 18g / in for light release surface, 65g / in for heavy release surface (180° peel, 25℃), with a release force difference of 47g / in.

[0062] 6. Preparation methods for roll materials (specifically improving film strength and dispersibility) Preparation of component A: Add 9 parts xylene to hydroxyl-terminated polydimethylsiloxane, stir at 25°C for 25 min, add silica and stir at 1500 rpm for 45 min, add modified graphene oxide and continue stirring at 1200 rpm for 40 min, then add the remaining components and the remaining 9 parts xylene, and stir for 1.5 h. Preparation of component B: Trimethylsiloxytriethoxysilane was added to xylene and stirred at 25°C for 25 min. Acetylacetone and dibutyltin dilaurate were added and stirred for 15 min. Modified perfluoropolyether-4 was added and stirred for 45 min. Paint mixing: Mix components A and B at a mass ratio of 1:0.12, stir at 900 rpm for 4 minutes, and let stand for 4 minutes; Roll preparation: In a cleanroom, the PP release film is laid flat with the release side facing up, and the coating is applied (110μm in one coat, and then applied in two coats to reach 220μm). After drying, it is rolled up, with a single roll length of 600m and a width of 1.5m.

[0063] 7. Construction Precautions After application, apply pressure with a heavy object for 30 minutes to ensure a tight bond between the protective film and the substrate, thereby improving adhesion strength. During application, avoid contact with the film to prevent scratches. Before complete curing (within 7 hours), avoid violent vibrations to ensure stable adhesion.

[0064] The embodiments of the present invention have the following advantages: Tough and wear-resistant: After modification, the tensile strength is increased by 50% and the wear resistance is improved by 55%, resisting external damage; Uniform dispersion: Modified graphene oxide has good compatibility with the coating system, with no agglomeration and stable performance; Construction adaptability: PP release film is wear-resistant and scratch-resistant, adaptable to complex construction environments, and avoids film contamination.

[0065] After testing, its protective film layer performance is as follows: elastic modulus 1.4MPa, average thickness 220μm, containing 5% modified graphene oxide; antifouling and mechanical properties: static antifouling reaches level 5 (no adhesion) after 12 months, adhesion level 3, tensile strength increased by 50%; abrasion resistance: can withstand 5N impact force, fishing net scratches without damage, and service life extended to 6 years.

[0066] Example 5 The environmentally friendly and efficient surface imitation fish skin protective material, construction method, and products provided in this embodiment are basically the same as those in Embodiments 1 to 4. The difference is that, in response to the problems of uncontrollable release and serious waste of traditional antifouling agents, it provides a pH-responsive intelligent imitation fish skin protective material to achieve intelligent and precise antifouling. It is mainly used in multi-condition vessels switching between nearshore and ocean-going, floating facilities on water, and other scenarios such as alternating berthing and navigation.

[0067] 1. Formulation of low-elasticity, low-surface-energy fish-skin-like coating Component A (parts by mass): 71 parts of hydroxyl-terminated polydimethylsiloxane, 22 parts of xylene, 3 parts of silicon dioxide (A200), 5 parts of iron oxide, 0.9 parts of nano cuprous oxide, and 1.1 parts of cuprous thiocyanate; Component B (parts by weight): 41 parts trimethylsiloxytriethoxysilane, 11.5 parts acetylacetone, 46.485 parts xylene, 0.015 parts dibutyltin dilaurate, and 1 part modified perfluoropolyether-5; pH-responsive microcapsules (3% of the total mass of the fish skin-like coating).

[0068] 2. Modified perfluoropolyether-5 formulation (specifically enhances intelligent response synergy) Based on modified perfluoropolyether-1, the amount of KH-570 silane coupling agent added was adjusted to 1g, and the reaction temperature in step A3 was controlled at 52℃ to optimize the synergistic effect of molecular structure and pH-responsive microcapsules.

[0069] 3. Adhesive formulation (suitable for various working conditions, stable curing) Components (parts by weight): 53 parts liquid epoxy resin (E-51), 47 parts polyamide curing agent (650), 4 parts silane coupling agent (KH-560), 9 parts n-butanol, 9 parts xylene, 2 parts accelerator (DMP-30); Performance parameters: surface drying time 38 min, initial curing time 2 h, complete curing time 7.5 h, excellent weather resistance.

[0070] 4. pH-responsive microcapsules (added separately, accounting for 3% of the total mass of the fish skin-like coating) Core material: 50 parts antifouling agent (cuprous thiocyanate); Wall material: 50 parts pH-sensitive chitosan-sodium alginate complex; Particle size 3-8μm, which breaks down and releases the antifouling agent at pH 6.0-7.5 (the metabolic range of marine microorganisms).

[0071] 5. Release film selection (matching weather resistance and precise peeling under various working conditions) Specific model: Dual silicone release film (PET substrate, thickness 50μm); Release force parameters: light release surface 22g / in, heavy release surface 75g / in (180° peel, 25℃), release force difference 53g / in; 6. Roll material preparation method (targeted protection of microcapsules and intelligent response function) Preparation of component A: Add 11 parts xylene to hydroxyl-terminated polydimethylsiloxane, stir at 25°C for 25 min, add silica and stir at 1500 rpm for 45 min, then add the remaining components and the remaining 11 parts xylene, and stir for 1.5 h; Preparation of component B: Trimethylsiloxytriethoxysilane was added to xylene and stirred at 25°C for 25 min. Acetylacetone and dibutyltin dilaurate were added and stirred for 15 min. Modified perfluoropolyether-5 was added and stirred for 45 min. Coating mixing: Mix components A and B at a mass ratio of 1:0.12, stir at 900 rpm for 4 minutes, let stand for 3 minutes, gently add pH-responsive microcapsules and stir for 1 minute; Roll preparation: In a cleanroom, the double silicone release film is laid flat with the release side facing up, and the coating is applied by roller (90μm in one coat, applied in two coats to reach 180μm). After drying, it is rolled up, with a single roll length of 400m and a width of 1m.

[0072] 7. Construction Precautions After construction, allow the membrane to cure indoors for 24 hours before water application to ensure stable bonding between the microcapsules and the membrane layer. Avoid applying excessive pressure during installation to prevent premature rupture of the microcapsules. Regularly check the integrity of the membrane layer and repair any damage promptly to prevent localized antifouling failure.

[0073] The embodiments of the present invention have the following characteristics: Intelligent Response: Microcapsules precisely release antifouling agents according to pH changes in marine microbial metabolism, increasing release by 25% when at rest and reducing it by 18% when at sea; Weather Stable: The dual-silicone release film has strong weather resistance, with release force fluctuation ≤5% in environments ranging from -10 to 60℃, making it suitable for various operating conditions; Environmentally Friendly and Efficient: Antifouling agent utilization is increased by 30%, meeting the latest IMO 2025 limit requirements.

[0074] After actual testing, its protective membrane performance is as follows: elastic modulus 1.1 MPa, average thickness 180 μm, containing 3% pH-responsive microcapsules; antifouling and intelligent performance: antifouling life up to 5.8 years, copper ion release meets IMO 2025 limits, pH response sensitivity ≥95%; actual results: no obvious adhesion after 3 months of stillness, drag reduced by 15% during navigation, and antifouling agent utilization rate increased by 30%.

[0075] Example 6 The environmentally friendly and efficient surface imitation fish skin protective material, construction method and product provided in this embodiment are basically the same as those in Embodiments 1 to 5. The difference is that a different connecting adhesive is used to provide more construction support.

[0076] The adhesive used in this embodiment is a two-component polyurethane adhesive, the formulation of which is shown in Table 1 below: Table 1

[0077] The mixing ratio of this adhesive is: A:B = 100:25~30 (calculated based on NCO / OH ≈ 1.1:1); surface drying time: 15~30 min; increasing the amount of solvent (butyl acetate) prolongs the surface drying time; initial curing time: 4~6 h (room temperature, under T-12 catalysis, NCO-OH reaction starts); complete curing time: 24~48 h (reaching final strength and crosslinking density).

[0078] Example 7 The environmentally friendly and efficient surface imitation fish skin protective material, construction method and product provided in this embodiment are basically the same as those in Embodiments 1 to 6. The difference is that the connecting adhesive used is different to provide more construction support.

[0079] The adhesive used in this embodiment is a two-component acrylic structural adhesive, the formulation of which is shown in Table 2 below: Table 2

[0080] The mixing ratio for this adhesive is: A:B = 100:5~8 (volume or mass ratio, prepare and use immediately); surface drying time: 5~15 min (increasing the amount of ethyl acetate solvent will extend the surface drying time); initial curing time: 30~60 min (redox initiation, rapid polymerization at room temperature); complete curing time: 4~8 h (reaching 90% strength).

[0081] Example 8 The environmentally friendly and efficient surface imitation fish skin protective material, construction method and product provided in this embodiment are basically the same as those in Embodiments 1 to 7. The difference is that the connecting adhesive used is different to provide support during underwater construction.

[0082] The adhesive used in this embodiment is a moisture-curing silicone-modified polyurethane adhesive (one-component), and its formulation and proportions are shown in Table 3 below: Table 3

[0083] The curing mechanism of this adhesive is as follows: the terminal silane (-Si(OCH3)3) reacts with moisture in the environment, hydrolyzing → condensing → crosslinking; surface drying time: 20~40 min (increasing the amount of butanol prolongs the surface drying time and is beneficial for defoaming and leveling); initial curing time: 2~4 h (a crosslinked layer forms on the surface, which can be touched); complete curing time: 24~72 h (deep curing, dependent on moisture diffusion).

[0084] Example 9 The environmentally friendly and efficient surface imitation fish skin protective material, construction method and product provided in this embodiment are basically the same as those in Embodiments 1 to 7. The difference is that the connecting adhesive used is different, so as to provide construction support for local small-area emergency repair and patching.

[0085] The adhesive used in this embodiment is cyanoacrylate (CA) quick-drying adhesive, and its formula and proportions are shown in Table 4 below: Table 4

[0086] The surface drying time of this adhesive is 30-60 seconds (the surface drying time will be extended when the amount of acetone is increased); the initial curing time is 1-3 minutes (when operational strength is achieved); and the complete curing time is 2-4 hours (when final strength is achieved).

[0087] The key features of the embodiments of this invention are the precise optimization of the formulations of components A and B of the protective coating, the scientific selection of the release film type and release force parameters, and the synergistic improvement of the preparation and construction processes. This achieves a simultaneous revolution in traditional materials and construction methods, simplifying the material structure to a two-layer roll material. Factory mass production is controllable, transportation and storage are convenient, and overall costs are significantly reduced. The protective film layer possesses low surface energy, high adhesion, and specific functions (self-healing, intelligent response, etc.), providing both dynamic and static antifouling protection, and extending its lifespan to 5-6.5 years. The construction process is simple and efficient, eliminating the need for multiple on-site coatings, and the release film can be easily peeled off without residue, making it suitable for various scenarios (new shipbuilding, old ship retrofitting, multi-condition vessels). It exhibits excellent environmental performance, with low VOC content and copper ion slow-release compliance, meeting IMO standards. Environmental standards; creatively proposes to shift from on-site spraying of liquid coatings to direct application of prefabricated roll materials in the factory, avoiding on-site pollution and achieving efficient industrial production; at the same time, it also has a major breakthrough in performance integration, adopting a minimalist material structure of release layer and protective film layer, which is easy to manufacture, transport and use, and does not require edge sealing, which can solve the problems of cracking and interface desorption of traditional plastic substrates.

[0088] This invention can be widely applied to ships or underwater navigation vehicles that require surface antifouling treatment, as well as water equipment and facilities. It has the advantages of fast construction speed, good antifouling effect, low overall cost, and environmental protection and high efficiency. It solves the problems of high on-site construction difficulty, unstable construction quality and poor environmental performance of existing ship antifouling coatings, and has good market application prospects and economic and social benefits.

[0089] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. An environmentally friendly and efficient surface fish-skin-imitating protective material, characterized in that, It is a roll material pre-prepared in a factory, including a release layer and an elastic low-surface energy fish-skin-like coating protective film layer, wherein the elastic low-surface energy fish-skin-like coating protective film layer is obtained by pre-coating a low-surface energy fish-skin-like coating on the release layer and drying, and then co-winding the release layer and the low-surface energy fish-skin-like coating to form a roll material continuously in the length direction.

2. The environmentally friendly and efficient surface sharkskin-imitating protective material according to claim 1, characterized in that, The average thickness of the elastic low-surface energy fish-skin-like coating protective film layer is 100-300 µm, and the elastic modulus E is 0.5 MPa≤E≤2.5 MPa, which is formed by directly coating the low-surface energy fish-skin-like coating on the release surface of the release layer and drying.

3. The environmentally friendly and efficient surface fish-skin-imitated protective material according to claim 1 or 2, characterized in that, The low-surface energy fish-skin-like coating is made of A component and B component. The A component includes the following raw materials by weight: 70-75 parts of hydroxyl-terminated polydimethylsiloxane, 15-25 parts of xylene, 2-4 parts of silicon dioxide, 2-5 parts of iron oxide, 0.5-1 part of nano-cuprous oxide, and 1-3 parts of cuprous thiocyanate; The B component includes the following raw materials by weight: 40-45 parts of trimethylsiloxy triethoxysilane, 10-12 parts of acetylacetone, 40-50 parts of xylene, 0.01-0.02 parts of organic tin, and 1-3 parts of modified perfluoropolyether.

4. The environmentally friendly and efficient surface sharkskin-imitating protective material according to claim 3, characterized in that, The modified perfluoropolyether is prepared by the following steps: A1, 2,2-difluoro-2-iodo-1-phenylethanone, benzaldehyde and indium powder are added to deionized water, and reacted at 45-55℃ for 2-3h, then extracted with ethyl acetate, the organic phase is combined and dried with anhydrous sodium sulfate for 60-90min, then separated by silica gel column chromatography, to obtain α,α-difluoro-β-hydroxy ketone; A2, α,α-difluoro-β-hydroxy ketone obtained in step A1 and acrylic acid are added to toluene, a catalyst is added, and reacted at 70-80℃ for 2-3h, then dried to obtain a compound; A3, vinyl-terminated perfluoropolyether, the compound obtained in step A2, KH-570 silane coupling agent, hexakis(3-mercaptopropionic acid) dipentaerythritol ester and azobisisobutyronitrile are added to hexafluoroisopropanol, and reacted at 50-60℃ for 2-4h, then rotary evaporated to obtain the modified perfluoropolyether.

5. The environmentally friendly and efficient surface sharkskin-imitating protective material according to claim 4, characterized in that, The elastic low-surface energy fish-skin-like coating protective film layer is prepared by the following steps: S1, hydroxyl-terminated polydimethylsiloxane is added to part of xylene, stirred at 20-30℃ for 20-30min, then silicon dioxide is added and stirred at high speed for 30-60min, then iron oxide, nano-cuprous oxide, cuprous thiocyanate and the remaining amount of xylene are added and stirred for 1-2h to obtain A component; S2, trimethylsiloxy triethoxysilane is added to xylene, stirred at 20-30℃ for 20-30min, then acetylacetone and organic tin are added and stirred for 10-20min, finally modified perfluoropolyether is added and stirred for 30-60min to obtain B component; S3, B component obtained in step S2 is added to A component obtained in step S1, stirred at 800-1000rpm for 3-5min, and then left to stand for 3-5min to obtain low-surface energy fish-skin-like coating. S4, uniformly coating the low surface energy fish skin imitation coating on the release surface of the release layer, and after curing and drying, an elastic low surface energy fish skin imitation coating protective film layer is obtained.

6. The environmentally friendly and efficient surface sharkskin-imitating protective material according to claim 1, characterized in that, The release layer is a double-sided release film, one side of the film is a light release surface and the other side is a heavy release surface, the low surface energy fish skin imitation coating is pre-coated on the heavy release surface and dried, and after winding, the outer side of the elastic low surface energy fish skin imitation coating protective film layer is in contact with the light release surface, forming a two-sided release film with different release forces of the elastic low surface energy fish skin imitation coating protective film layer.

7. A method for preparing an environmentally friendly and efficient surface fish-skin-imitating protective material, characterized in that, It is used for preparing the ship surface fish skin imitation protective material according to any one of claims 1 to 6, which comprises the following steps: B1, preparing an elastic low surface energy fish skin imitation coating and a double-sided release film in advance; B2, continuously unwinding and laying the double-sided release film roll on the production line, with the heavy release surface upward; B3, uniformly coating the elastic low surface energy fish skin imitation coating on the heavy release surface, drying, and when the thickness of the coating film obtained by single coating does not reach 100-300 µm, performing second or multiple coating; B4, bonding the dried coating film on the heavy release surface to form an elastic low surface energy fish skin imitation coating protective film layer, and the double-sided release film forms a release layer, and finally winding the elastic low surface energy fish skin imitation coating protective film layer and the release layer concentrically to obtain a rolled environmentally friendly and efficient ship surface fish skin imitation protective material.

8. The production method according to claim 7, characterized by, The steps B2 to B4 are carried out in a dust-free workshop, and the coating process in step B3 is blade coating or roller coating.

9. An environmentally friendly and efficient surface fish-skin-imitating protective construction method, characterized in that, It uses the rolled environmentally friendly and efficient surface fish skin imitation protective material according to any one of claims 1 to 6, which comprises the following steps: C1, pretreating the construction outer surface of the ship or water equipment to remove oil stains, rust and impurities, and air drying; C2, uniformly coating the prepared connecting adhesive on the outer surface of the ship to form a ship surface connecting layer; C3, after coating the connecting adhesive, unwinding the protective film layer of the rolled environmentally friendly and efficient ship surface fish skin imitation protective material with the outer surface of the protective film layer facing the ship surface connecting layer, and applying pressure from the light release surface side to make the protective film layer tightly adhere to the ship surface connecting layer; C4, allowing the connecting adhesive to continue to cure at room temperature, and when the bonding strength between the protective film layer and the ship surface connecting layer is greater than the bonding strength between the inner surface of the protective film layer and the heavy release surface, peeling off the release layer from the outside along the direction parallel to the extension plane of the ship surface to expose the inner surface of the protective film layer outward, and forming a low surface energy fish skin imitation coating protective surface bonded to the ship surface.

10. The environmentally friendly and efficient surface fish-skin-imitating protective construction method according to claim 9, characterized in that, The connecting adhesive is one of two-component epoxy resin adhesive, two-component polyurethane adhesive, moisture-curable silicone-modified polyurethane adhesive, two-component acrylate adhesive, or cyanoacrylate quick-drying adhesive.

11. An environmentally friendly and efficient surface imitation fish skin protective product, characterized by, It is a product obtained by using the surface fish skin imitation protective material according to any one of claims 1 to 6 or the surface fish skin imitation protective construction method according to any one of claims 9 to 10.

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