Antifouling paint as well as preparation method and application thereof

Abstract

The invention relates to the technical field of marine antifouling coatings, in particular to an organic-inorganic composite antifouling coating as well as a preparation method and application thereof. The antifouling paint comprises a component A and a component B in a weight ratio of (7-9): 1, and the component A comprises the following raw materials in parts by weight: 50-75 parts of hydroxyl organic silicon resin and 5-20 parts of an antifouling agent; the component B is prepared from the following raw materials in parts by weight: 10 to 30 parts of modified organic silicon resin, 20 to 80 parts of silica gel and 1 to 10 parts of auxiliaries; the hydroxyl organic silicon resin is dihydroxy-terminated silicone oil, and the content of hydroxyl in the hydroxyl organic silicon resin is 0.025-3wt%. The invention provides a low-surface-energy antifouling coating applied to a marine ship. The coating is provided with a low-surface-energy surface and a hydrogel surface which are uniformly staggered. The low-surface-energy antifouling coating is good in paint film elasticity, low in surface tension, good in impact resistance and high in scratch resistance, and the effective service life of the low-surface-energy antifouling coating is as long as seven years or above.

Description

Technical Field

[0001] The invention relates to the technical field of marine antifouling coatings, and in particular to an organic-inorganic composite antifouling coating and a preparation method and application thereof. Background Art

[0002] Antifouling paints suitable for all ships in the marine environment, including steel ships, aluminum ships, etc., should not contain organic tin compounds, and must be environmentally friendly, non-toxic, and have no irritating odor, and have a long antifouling period.

[0003] Existing marine ship antifouling mainly adopts dissolving antifouling paint, self-polishing antifouling paint and low surface energy antifouling paint. Dissolving antifouling paint is mainly composed of rosin, resin (chlorinated rubber), antifouling agent, additive, pigment and solvent; in the early stage of dissolving antifouling paint, due to the dissolution of rosin, the antifouling agent is released, and the antifouling effect is good. Generally, the antifouling period is about 1 year. Dissolving antifouling paint is mainly used on fishing boats. Self-polishing antifouling paint is mainly composed of rosin, self-polishing resin (acrylic resin, silicone resin), antifouling agent, additive, pigment and solvent. Self-polishing antifouling paint is the mainstream product of antifouling paint at present. The release of mature product antifouling agent is relatively stable, and the antifouling effect is good. The antifouling effect is generally 3-5 years. At present, most commercial ships use self-polishing antifouling paint. However, self-polishing antifouling paint mainly relies on the polishing of ship speed. Ships need to choose different self-polishing antifouling paints according to the speed of the ship. Low surface energy antifouling paint is a new generation of environmentally friendly antifouling paint. International brands such as Haihong X3 do not contain antifouling agents. They mainly rely on the ultra-low surface tension of the coating surface and the characteristics of marine organisms being difficult to attach to prevent fouling. In actual applications, it is difficult to achieve long-term antifouling, and the antifouling period is short (3-5 years).

[0004] Patent CN118064055A discloses a water-based organic silicon corrosion-resistant and antifouling transparent coating in marine environment and its preparation method and application. The invention uses water-based epoxy modified organic silicon resin, silane coupling agent as curing agent, and carboxylated graphene oxide as antibacterial factor to produce an antifouling coating. However, the coating has little effect on the attachment of marine organisms, and carboxylated graphene oxide is difficult to inhibit the growth of marine organisms. In addition, the service life is short, and it will not play an effective antifouling role in 2-3 years. Summary of the invention

[0005] The purpose of the present invention is to provide an antifouling coating with a long effective antifouling period and a preparation method and application thereof.

[0006] In order to achieve the above object, the technical solution of the present invention is as follows:

[0007] An antifouling coating, the raw materials of which include component A and component B in a weight ratio of (7-9):1, wherein component A includes the following raw materials in weight: 50-75 parts of hydroxyl silicone resin and 5-20 parts of antifouling agent;

[0008] Component B includes the following raw materials in parts by weight: 10-30 parts of modified silicone resin, 20-80 parts of silicone gel and 1-10 parts of auxiliary agent;

[0009] The hydroxyl organic silicone resin is a di-terminal hydroxyl silicone oil, and the hydroxyl content in the hydroxyl organic silicone resin is 0.025-3wt%.

[0010] If the hydroxyl value is too large, the molecular weight will be too small and the paint film will be brittle; if the hydroxyl value is too small, the molecular weight will be large, the viscosity will be large and the fluidity will be poor.

[0011] In a preferred embodiment, in the B component, the raw materials of the silicone gel include 20-60 parts of silane, 0.2-10 parts of acid solution, and 30-70 parts of solvent.

[0012] In a preferred embodiment, the silane is ethyl orthosilicate.

[0013] In a preferred embodiment, the acid solution is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, and benzoic acid solutions, preferably at least one of hydrochloric acid solution, sulfuric acid solution, and acetic acid solution.

[0014] In a preferred embodiment, the solvent is one of ethanol and methanol.

[0015] In a preferred embodiment, the preparation method of the silicone gel in the B component includes: dissolving silane in a solvent, adding an acid solution dropwise, and stirring the reaction for 13-30 hours to obtain the silicone gel.

[0016] In a preferred embodiment, the mass concentration of the acid solution is 30-37%.

[0017] In a preferred embodiment, component A further comprises: 2-20 parts of pigment, 0-10 parts of filler and 5-30 parts of solvent.

[0018] In a preferred embodiment, component B further comprises: 10-40 parts of solvent.

[0019] In a preferred embodiment, the viscosity of the hydroxy silicone resin is 50-5000 Pa.s.

[0020] If the viscosity is too high and the molecular weight is too large, the construction performance will be greatly affected and the leveling will be poor; if the molecular weight is too small, it will also be not conducive to the product construction.

[0021] In a preferred embodiment, in the component A, the antifouling agent is at least one of cuprous oxide, copper pyrithione, and DCOIT.

[0022] In a preferred embodiment, in the component A, the pigment is at least one of red iron oxide, titanium dioxide, yellow iron oxide, cobalt blue, cobalt green, titanium nickel yellow, carbon black, copper chrome black, iron black, phthalocyanine blue, phthalocyanine green, and scarlet pigment.

[0023] In a preferred embodiment, in the component A, the filler is at least one of silicon dioxide, feldspar powder, talc, barium sulfate, and fumed silica, preferably at least one of silicon dioxide and barium sulfate.

[0024] In a preferred embodiment, in the component A, the solvent is at least one of xylene, ethanol, acetylacetone, n-butanol and isobutanol.

[0025] In a preferred embodiment, in the B component, the modified silicone resin is at least one of epoxy polyether modified silicone resin, polyethylene glycol modified silicone resin, polyether amine modified silicone resin, and polyether modified silicone resin, preferably polyether modified silicone resin or polyether modified hydrogenated silicone resin.

[0026] In a preferred embodiment, in the component B, the auxiliary agent is at least one of organotin, organotin chelate, titanate, titanium chelate, ferric acetylacetonate, and aluminum acetylacetonate, preferably at least one of organotin, organotin chelate, ferric acetylacetonate, and aluminum acetylacetonate.

[0027] In a preferred embodiment, in the component B, the solvent is at least one of xylene, toluene, trimethylbenzene, ethanol, propylene glycol methyl ether, n-butanol, isobutanol, acetylacetone, and butanone oxime, preferably at least one of xylene, acetylacetone, and butanone oxime.

[0028] Based on the same inventive concept, the present invention also claims a method for preparing the antifouling coating, comprising the following steps:

[0029] Preparation of component A: First, stir the hydroxy silicone resin and part of the solvent evenly, then add the pigment, antifouling agent and filler under stirring, and disperse for 20-30 minutes to obtain a slurry; then, sand grind the slurry to a fineness of ≤20μm, and add the remaining solvent;

[0030] Preparation of component B: Mix the inorganic gel, solvent and additives evenly, and then add the modified silicone resin under stirring;

[0031] The component A and the component B are mixed evenly according to a certain proportion to obtain the antifouling coating.

[0032] In a preferred embodiment, the stirring speed is 400-800 rpm / min.

[0033] The third object of the present invention is to provide the application of the antifouling coating on the bottom of a ship, specifically spraying the coating on the bottom of a ship to improve its antifouling and anti-microbial adhesion properties.

[0034] The purpose of the present invention is to provide a low surface energy antifouling coating for use in marine vessels, wherein the coating has a uniformly staggered low surface energy surface and a hydrogel surface, the hydrogel coating has properties similar to those of contact lenses, the film layer has a smooth appearance, but microscopically, the film layer has a relatively large number of small-area hydrophilic film layers, water vapor in the hydrophilic film layer can be slowly infiltrated and discharged, and the low surface energy antifouling coating has good film elasticity, low surface tension, good impact resistance, and high scratch resistance.

[0035] Specifically, the technical solution of the present invention adopts a method of combining low surface tension of the coating as the main component, hydrogel technology and fungicide as the auxiliary component to jointly solve the problem of short antifouling period of low surface energy antifouling paint. The present invention is further explained below:

[0036] The antifouling coating of the present invention is composed of ultra-low surface energy hydroxyl silicone resin, oligomeric inorganic silicone gel, and hydrophilic polyether segment substances. The low surface energy hydroxyl silicone resin and the ultra-low surface tension oligomeric inorganic silicone gel undergo condensation reaction to form a three-dimensional seaweed structure, providing an ultra-low surface energy hydrophobic partial coating; the polyether segment-modified silicone resin is evenly embedded in the pores of the three-dimensional seaweed structure, providing a hydrophilic partial surface, the polyether segment part slowly dissolves in the seawater, and the silicone part combines with water to form a hydrogel; because the coating is mixed during the coating construction, these components become a uniform three-dimensional dispersion, and after film formation and drying, it is a uniform coating. From a microscopic point of view, the hydrophobic inorganic silica gel structure and the polyether silicone structure segments of the coating are evenly interlaced, so that a coating film with an ultra-low surface energy structure as the main part and a hydrophilic structure dotted therein is formed in the seawater, forming a silicone elastomer similar to a contact lens. After the coating is used, the hydrophilic polyether chain segments absorb water to form a microporous hydrogel layer. The microporous hydrogel layer will produce extremely slow material exchange. The in and out of water will bring out the antifouling agent and polyether silicone. The polyether silicone part and the antifouling agent will further continue to combine into a hydrogel surface; a new hydrogel film layer with an antifouling agent is formed on the surface of the hydrophilic part. The hydrophilic gel film layer not only contains a high concentration of antifouling agent, but also can prevent bacteria from growing and preventing fouling, thereby destroying the growth environment of marine organisms, thereby preventing marine organisms from growing and forming on the coating surface, and preventing the hydrophobic low surface energy part from being attached by marine organisms after a long time. Due to the low surface tension of the coating, marine organisms are not easy to attach to the hydrophobic part. Due to the low surface energy design, the main body of the coating is an ultra-low surface tension silicone coating, and the super-hydrophobic structure of the matrix resin in the coating structure accounts for more than 95% of the coating, so the coating exhibits ultra-low surface tension and extremely strong hydrophobic properties. Theoretically, the water contact angle of the pure inorganic silicone coating can reach more than 150°, and the hydrophilic part will reduce the water contact angle. According to actual measurements, the contact angle of the anti-fouling coating of the present invention with water reaches more than 110°. The coating as a whole exhibits excellent marine biological desorption ability, and the effective service life is more than seven years, which effectively reduces the resistance of ships in navigation for a long time, thereby reducing energy consumption and increasing speed, which can reduce energy consumption by more than 10%. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is further described below in conjunction with specific embodiments. In the following implementation, the antifouling coating prepared by the present invention is applied to the painting of ships.

[0038] Example 1

[0039] Preparation of antifouling coatings:

[0040] Preparation of component A: 6.3 kg of hydroxy silicone resin (Dow Corning's 4010, the hydroxyl content of the hydroxy silicone resin is 0.025-0.03 wt%) is added to a disperser, 1.4 kg of xylene is added at a speed of 500 rpm, and after mixing evenly, 0.9 kg of pyridinethione and 0.9 kg of red iron oxide are added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of xylene is added, and the material is discharged for use.

[0041] Preparation of component B:

[0042] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0043] 1) Preparation of acid solution: Add 97.3 kg of 37% hydrochloric acid and 2.7 kg of water into the solvent, stir evenly and set aside.

[0044] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg of ethanol and 5.6 kg of ethyl orthosilicate into a container, stir at 500 rpm, add 0.4 kg of hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0045] Preparation of component B: Add 5 kg of oligomeric inorganic silica gel solution into a container, add 1.8 kg of xylene, 1 kg of 10% dibutyltin laurate, and 2.2 kg of Dow Corning DC57, and mix well.

[0046] The component A and the component B are uniformly mixed in a weight ratio of 8:1 to obtain an antifouling coating.

[0047] The application method of antifouling coating is as follows:

[0048] After degreasing the sandblasted steel plate, apply 220μm of general epoxy primer and 100μm of silicone antifouling paint tie paint. Mix component A and component B at a ratio of 8:1 (mass ratio) and spray the paint on the silicone antifouling paint tie paint. The dry film is 200μm, the wet film is 285μm, and the dosage is 0.3kg / m 2 , cure at room temperature for 24 hours to form an antifouling coating.

[0049] Example 2

[0050] Preparation of antifouling paint:

[0051] Preparation of component A: 5 kg of hydroxy silicone resin (Dow Corning's 4010, the hydroxy content of the hydroxy silicone resin is 0.025-0.03 wt%) is added to a disperser, 2.0 kg of acetylacetone is added at a speed of 500 rpm, and after mixing evenly, 1.5 kg of pyridinethione, 0.8 kg of red iron oxide, and 0.2 kg of silicon dioxide are added and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of acetylacetone is added, and the material is discharged for use.

[0052] Preparation of component B:

[0053] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0054] 1) Preparation of acid solution: Add 98 kg of 37% hydrochloric acid and 2 kg of water into the solvent, stir evenly and set aside.

[0055] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg ethanol and 5.0 kg ethyl orthosilicate into a container, stir at 500 rpm, add 0.3 kg hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0056] Preparation of component B1: Add 5 kg of oligomeric inorganic silica gel solution into a container, add 1.2 kg of xylene, 2 kg of 10% dibutyltin laurate, and 1.8 kg of Dow Corning DC57, and mix well.

[0057] The coating method of the antifouling coating of this embodiment is the same as the application method described in Example 1.

[0058] Example 3

[0059] Preparation of antifouling paint:

[0060] Preparation of component A: 7.5 kg of hydroxy silicone resin (Dow Corning's 0156, the hydroxy content of the hydroxy silicone resin is 2.5-3 wt%) is added to a disperser, 0.7 kg of ethanol is added at a speed of 500 rpm, and after mixing evenly, 0.8 kg of pyridinethione and 0.5 kg of red iron oxide are added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of ethanol is added, and the material is discharged for use.

[0061] Preparation of component B:

[0062] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0063] 1) Preparation of acid solution: Add 96.4 kg of 37% hydrochloric acid and 3.6 kg of water into the solvent, stir evenly and set aside.

[0064] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg of ethanol and 5.6 kg of ethyl orthosilicate into a container, stir at 500 rpm, add 0.4 kg of hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0065] Preparation of component B: Add 6 kg of oligomeric inorganic silica gel solution into a container, add 1 kg of xylene, 1.5 kg of 10% dibutyltin laurate, and 1.5 kg of Dow Corning DC57, and mix well.

[0066] The coating method of the antifouling coating of this embodiment is the same as the application method described in Example 1.

[0067] Example 4

[0068] Preparation of antifouling paint:

[0069] Preparation of component A: 6 kg of hydroxy silicone resin (Dow Corning's 0156, the hydroxyl content of the hydroxy silicone resin is 2.5-3 wt%) is added to a disperser, 1.2 kg of n-butanol is added at a speed of 500 rpm, and after mixing evenly, 1.2 kg of pyridinethione and 1.1 kg of red iron oxide are added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 n-butanol is added, and the material is discharged for use.

[0070] Preparation of component B:

[0071] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0072] 1) Preparation of acid solution: Add 99 kg of 37% hydrochloric acid and 1 kg of water into the solvent, stir evenly and set aside.

[0073] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg of ethanol and 5.6 kg of ethyl orthosilicate into a container, stir at 500 rpm, add 0.5 kg of hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0074] Preparation of component B: Add 5.5 kg of oligomeric inorganic silica gel solution into a container, add 0.5 kg of xylene, 2 kg of 10% dibutyltin laurate, and 2 kg of Dow Corning DC57, and mix well.

[0075] The antifouling coating coating method of this embodiment is the same as the use method described in Example 1.

[0076] Comparative Example 1

[0077] The difference between this comparative example and Example 1 is that, instead of adding an oligomeric inorganic silica gel solution, an equivalent amount of ethyl orthosilicate is added in this comparative example.

[0078] Preparation of antifouling paint:

[0079] Preparation of component A: 6.3 kg of hydroxy silicone resin (Dow Corning's 4010, the hydroxyl content of the hydroxy silicone resin is 0.025-0.03 wt%) is added to a disperser, 1.4 kg of xylene is added at a speed of 500 rpm, and after mixing evenly, 0.9 kg of pyridinethione and 0.9 kg of red iron oxide are added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of xylene is added, and the material is discharged for use.

[0080] Preparation of component B:

[0081] 6.4 kg of ethanol and 5.6 kg of ethyl orthosilicate were mixed evenly to obtain a ethyl orthosilicate solution.

[0082] Preparation of component B: Add 5 kg of ethyl orthosilicate solution into a container, add 1.8 kg of xylene, 1 kg of 10% dibutyltin laurate, and 2.2 kg of Dow Corning DC57, and mix well.

[0083] The coating method of the antifouling coating of this comparative example is the same as the method of use described in Example 1.

[0084] Comparative Example 2

[0085] The difference between this comparative example and Example 1 is that, in this comparative example, hydroxyl organic silicone resin is not added, but an equivalent methyl organic silicone resin is added.

[0086] Preparation of component A: 6.3 kg of methyl silicone resin (Dow Corning PMX200) was added into a disperser, 1.4 kg of xylene was added at a speed of 500 rpm, and after mixing evenly, 0.9 kg of pyridinethione and 0.9 kg of red iron oxide were added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of xylene was added, and the material was discharged for use.

[0087] Preparation of component B:

[0088] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0089] 1) Preparation of acid solution: Add 97.3 kg of 37% hydrochloric acid and 2.7 kg of water into the solvent, stir evenly and set aside.

[0090] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg of ethanol and 5.6 kg of ethyl orthosilicate into a container, stir at 500 rpm, add 0.4 kg of hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0091] Preparation of component B: Add 5 kg of oligomeric inorganic silica gel solution into a container, add 1.8 kg of xylene, 1 kg of 10% dibutyltin laurate, and 2.2 kg of Dow Corning DC57, and mix well.

[0092] The coating method of the antifouling coating of this comparative example is the same as the method of use described in Example 1.

[0093] Comparative Example 3

[0094] The difference between this comparative example and Example 1 is that, in this comparative example, no modified silicone resin is added, but an equivalent silicone resin KH550 is added.

[0095] Preparation of antifouling paint:

[0096] Preparation of component A: 6.3 kg of hydroxy silicone resin (Dow Corning's 4010, the hydroxyl content of the hydroxy silicone resin is 0.025-0.03 wt%) is added to a disperser, 1.4 kg of xylene is added at a speed of 500 rpm, and after mixing evenly, 0.9 kg of pyridinethione and 0.9 kg of red iron oxide are added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of xylene is added, and the material is discharged for use.

[0097] Preparation of component B:

[0098] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0099] 1) Preparation of acid solution: Add 97.3 kg of 37% hydrochloric acid and 2.7 kg of water into the solvent, stir evenly and set aside.

[0100] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg of ethanol and 5.6 kg of ethyl orthosilicate into a container, stir at 500 rpm, add 0.4 kg of hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0101] Preparation of component B: Add 5 kg of oligomeric inorganic silica gel solution into a container, add 1.8 kg of xylene, 1 kg of 10% dibutyltin laurate, and 2.2 kg of KH550, and mix well.

[0102] The coating method of the antifouling coating of this comparative example is the same as the method of use described in Example 1.

[0103] Comparative Example 4

[0104] The difference between this comparative example and Example 1 is that no hydroxyl silicone resin is added in this comparative example.

[0105] Preparation of antifouling paint:

[0106] Preparation of component A: Add 1.4 kg of xylene into a disperser, add 0.9 kg of pyrithione and 0.9 kg of red iron oxide at a speed of 500 rpm, and stir at high speed for 25 minutes; then sand grind to a fineness of ≤25 μm, add 0.5 kg of xylene, and discharge for later use.

[0107] Preparation of component B:

[0108] (1) Preparation of homemade oligomeric inorganic silica gel solution:

[0109] 1) Preparation of acid solution: Add 97.3 kg of 37% hydrochloric acid and 2.7 kg of water into the solvent, stir evenly and set aside.

[0110] 2) Preparation of oligomeric inorganic silica gel solution: Add 6 kg of ethanol and 5.6 kg of ethyl orthosilicate into a container, stir at 500 rpm, add 0.4 kg of hydrochloric acid solution while stirring, seal and place for 24 hours for use.

[0111] Preparation of component B: Add 5 kg of oligomeric inorganic silica gel solution into a container, add 1.8 kg of xylene, 1 kg of 10% dibutyltin laurate, and 2.2 kg of Dow Corning DC57, and mix well.

[0112] The coating method of the antifouling coating of this comparative example is basically the same as the method of use described in Example 1.

[0113] Comparative Example 5

[0114] The difference between this comparative example and Example 1 is that the oligomeric inorganic silica gel solution is not added in this comparative example.

[0115] Preparation of component A: 6.3 kg of hydroxy silicone resin (Dow Corning's 4010, the hydroxyl content of the hydroxy silicone resin is 0.025-0.03 wt%) is added to a disperser, 1.4 kg of xylene is added at a speed of 500 rpm, and after mixing evenly, 0.9 kg of pyridinethione and 0.9 kg of red iron oxide are added, and stirred at high speed for 25 minutes; then sand-milled to a fineness of ≤25 μm, 0.5 kg of xylene is added, and the material is discharged for use.

[0116] Preparation of component B:

[0117] Preparation of component B: Add 1.8 kg of xylene into a container, add 1 kg of 10% dibutyltin laurate and 2.2 kg of Dow Corning DC57, and mix well.

[0118] The antifouling coatings prepared in Examples 1-4 and Comparative Examples 1-5 were subjected to performance tests on the formed paint films and compared with commercially available low surface energy coatings. The commercially available low surface energy antifouling coatings were used according to the method described in Example 1. Specific performance test data are shown in Table 1:

[0119] Table 1 Antifouling coating performance test indicators

[0120]

[0121]

[0122] Among them, some comparative examples cannot be cured, such as comparative example 5.

[0123] According to Table 1, the antifouling performance is reduced when using non-oligomeric inorganic silicone gel curing agent; the performance is very poor when using other types of silicone resin; the antifouling performance is greatly reduced when using non-polyether silicone; the above comparison shows that the antifouling performance of the ultra-low surface energy coating, hydrophilic hydrogel and antifouling agent combined coating is excellent, indicating that the improvement of the present invention is helpful to improve the antifouling performance. The antifouling coating prepared by the method of the present invention has a higher solid content and lower VOC than similar products on the market. The dynamic simulation test is better than the commercially available products. The dynamic simulation test is more than 8 cycles, and the effective service life is more than 7 years, which can fully meet the requirements of ship antifouling coatings.

[0124] The above-described embodiments are intended to further illustrate the technical content of the present invention, but do not mean that the embodiments of the present invention are limited to these. Without departing from the principles of the present invention, any modification or technical extension made based on the present invention shall be deemed to be within the protection scope of the present invention.

Claims

1. An antifouling coating, characterized in that: The raw materials include component A and component B in a weight ratio of (7-9):1, wherein component A includes the following raw materials in weight: 50-75 parts of hydroxyl organic silicone resin and 5-20 parts of antifouling agent; Component B includes the following raw materials in parts by weight: 10-30 parts of modified silicone resin, 20-80 parts of silicone gel and 1-10 parts of auxiliary agent; The hydroxyl organic silicone resin is a di-terminal hydroxyl silicone oil, and the hydroxyl content in the hydroxyl organic silicone resin is 0.025-3wt%.

2. The antifouling coating according to claim 1, characterized in that: In the B component, the raw materials of the silicone gel include 20-60 parts of silane, 0.2-10 parts of acid solution, and 30-70 parts of solvent.

3. The antifouling coating according to claim 2, characterized in that: The silane is ethyl orthosilicate; the acid solution is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid and benzoic acid solutions; the mass concentration of the acid solution is 30-37%; and the solvent is one of ethanol and methanol.

4. The antifouling coating according to claim 2, characterized in that: In the B component, the preparation method of the silica gel comprises: dissolving silane in a solvent, adding an acid solution dropwise, and stirring the reaction for 13-30 hours to obtain the silica gel.

5. The antifouling coating according to claim 1, characterized in that: Component A also includes: 2-20 parts of pigment, 0-10 parts of filler and 5-30 parts of solvent; component B also includes: 10-40 parts of solvent.

6. The antifouling coating according to any one of claims 1 to 5, characterized in that: The viscosity of the hydroxy silicone resin is 50-5000 Pa.s.

7. The antifouling coating according to claim 6, characterized in that: In the component A, the antifouling agent is at least one of cuprous oxide, copper pyridinethione, and DCOIT; the pigment is at least one of red iron oxide, titanium dioxide, yellow iron oxide, cobalt blue, cobalt green, titanium nickel yellow, carbon black, copper chrome black, iron black, phthalocyanine blue, phthalocyanine green, and scarlet pigment; the filler is at least one of silicon dioxide, feldspar powder, talc, barium sulfate, and fumed silica, preferably at least one of silicon dioxide and barium sulfate; the solvent is at least one of xylene, ethanol, acetylacetone, n-butanol, and isobutanol.

8. The antifouling coating according to claim 6, characterized in that: In the B component, the modified silicone resin is at least one of epoxy polyether modified silicone resin, polyethylene glycol modified silicone resin, polyether amine modified silicone resin, and polyether modified silicone resin; the auxiliary agent is at least one of organotin, organotin chelate, titanate, titanium chelate, ferric acetylacetonate, and aluminum acetylacetonate; and the solvent is at least one of xylene, toluene, trimethylbenzene, ethanol, propylene glycol methyl ether, n-butanol, isobutanol, acetylacetone, and butanone oxime.

9. The method for preparing the antifouling coating according to any one of claims 1 to 8, characterized in that: The following steps are involved: Preparation of component A: First, stir the hydroxy silicone resin and part of the solvent evenly, then add the pigment, antifouling agent and filler under stirring, and disperse for 20-30 minutes to obtain a slurry; Then, the slurry was sand-milled to a fineness of ≤20 μm and the remaining solvent was added; Preparation of component B: Mix the inorganic gel, solvent and additives evenly, and then add the modified silicone resin under stirring; The component A and the component B are mixed evenly according to a certain proportion to obtain the antifouling coating.

10. Use of the antifouling coating according to any one of claims 1 to 8 in antifouling of the bottom of a ship.

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