Stain resistance-release coating composition, coating and preparation method and application thereof

Abstract

The invention discloses a fouling resistance-release type coating composition, a coating and a preparation method and application of the fouling resistance-release type coating composition. The coating composition comprises a first component and a second component, wherein the first component comprises an epoxy modified polysiloxane prepolymer, and the second component comprises a polyether modified isocyanate cross-linking agent. The fouling resistance-release coating composition and the polyurethane epoxy modified organosilicon hydrogel fouling resistance-release coating provided by the invention have excellent dynamic / static antifouling capability, and meanwhile, the construction method of the coating composition is simple and convenient, and the coating composition has an application prospect in the field of marine antifouling engineering.

Description

Technical Field

[0001] The invention belongs to the technical field of antifouling, and in particular relates to a fouling resistance-releasing coating composition, a coating, and a preparation method and application thereof. Background Art

[0002] The harm and losses caused by marine biofouling to human marine activities and marine economic industries are becoming increasingly prominent. On the one hand, biofouling will increase the roughness of the ship's surface, resulting in a significant increase in the ship's navigation resistance, a decrease in speed, an increase in fuel consumption, and an increase in transportation costs. Studies have shown that when the fouling degree of the hull surface reaches 5%, its fuel consumption will increase by 10%. On the other hand, fouling organisms will produce destructive tension and secrete organic acidic substances during the process of attachment, fouling and metabolism, destroying the paint film on the bottom of the ship, inducing and accelerating acid corrosion of steel plates and underwater facilities, further aggravating ship damage, shortening the service life of ships, and increasing the frequency of ship and dock maintenance. In addition, the adhesion and growth of attached organisms in seawater pipeline systems such as nuclear power plants, tidal power generation and seawater desalination will reduce the water flow rate in the pipeline, and even cause serious consequences such as system blockage, damage and safety accidents. According to incomplete statistics, the economic losses caused by marine biofouling worldwide can reach tens of billions of dollars each year.

[0003] Preventing biofouling is an important way to reduce the resistance of ships, prevent biocorrosion of marine equipment, and reduce energy consumption. In the 1970s, tributyltin-based marine antifouling coatings were developed, which have good antifouling and construction performance. However, due to its long-term toxicity to non-target organisms and serious damage to the marine ecological environment, it has been banned worldwide since 2008. Silicone coatings have low surface energy and elastic modulus, and the adhesion of fouling organisms on their surfaces is very weak. They are easily removed by the shear force generated by water flow. They have non-toxic and self-cleaning properties and are a very promising marine antifouling coating. Patent US6265515B1 involves a curable fluorinated silicone resin to improve the self-release ability of fouling on the surface of pure silicone resin coatings. It is formed by replacing some SiH groups in silicone resins with fluoroalkyl groups, and the remaining unreacted SiH groups are converted into Si-OH groups or Si-OR groups for cross-linking. The converted groups can react with added water, trialkoxymethylsilane or tetraalkoxysilane to form elastic network polymers. This type of organic silicon coating exhibits good antifouling ability on the surface of moving ships, but has poor antifouling ability during the period when the ship is moored and other relatively static application environments. WO2007053163A2 discloses an improved siloxane-based antifouling material, whose resin includes one or more copolymers (such as block copolymers, graft copolymers, etc.) in a suitable number, and such copolymers can be grafted with one or more polymer chains (including polysiloxane) onto the polysiloxane main chain, and these graft polymers can carry biocidal groups to provide biocidal and / or fouling release properties. This type of antifouling coating can provide short-term static antifouling ability, but has poor long-term antifouling ability.

[0004] Hydrogel is a high molecular polymer with a three-dimensional interconnected network structure. It is highly absorbent and insoluble in water. In a water environment, hydrogel has good antifouling properties due to the dense water molecule layer on the surface and the unstable surface due to the low elastic modulus. This is the same antifouling effect as the hydrogel layer formed by the mucus secreted by the epidermis of marine organisms. It is non-toxic and environmentally friendly, smooth, flowable and easy to peel after absorbing water. Therefore, hydrogel can be used as an antifouling coating for design and research. However, after the hydrogel absorbs water, the structure becomes loose, the softness increases, the strength is greatly reduced, it is easily destroyed by external forces and does not adhere to the substrate. This defect greatly limits the application of hydrogel in the field of antifouling coatings.

[0005] Patents WO2008132196A1, W02011076856A1, WO2013000478A1 and WO2013000477A1 combine the fouling self-release ability of silicone and the fouling resistance ability of hydrogel to develop a polysiloxane-based fouling control coating system, which includes a biocide and one or more hydrophilic segment-modified polysiloxanes, and controls the leaching of the biocide by combining the biocidal component in the antifouling coating with the silicon-based defouling coating to extend the biofouling-free period of the silicon-based coating, thereby obtaining a fouling-free, low-friction surface while using a relatively small amount of biocide. This type of silicone-based hydrogel antifouling coating combines the fouling release of silicone-based antifouling coatings, the high fouling resistance of hydrogels, and the biocidal effect of antifouling agents, and the coating will remain foul-free for a longer time than conventional silicone-based fouling release coatings. However, due to the characteristics of silicone hydrogel resins, this type of silicone hydrogel antifouling coating has the disadvantages of poor strength and poor adhesion to the substrate. During the coating process, silicone hydrogel resins dry slowly and have high requirements for substrate construction. During service in the marine environment, the surface hydrogel layer is more easily damaged or damaged by environmental degradation and cracking than the silicone part, resulting in unstable surface layer state and insufficient antifouling ability. Therefore, providing a coating that is simple to construct and has good antifouling ability is an urgent problem to be solved. Summary of the invention

[0006] The main purpose of the present invention is to provide a fouling resistance-releasing coating composition, coating and preparation method and application thereof, so as to overcome the shortcomings of the prior art.

[0007] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0008] An embodiment of the present invention provides a fouling resistance-release coating composition, which includes a first component and a second component; wherein the first component includes an epoxy-modified polysiloxane prepolymer, and the second component includes a polyether-modified isocyanate crosslinker.

[0009] In some specific embodiments, the epoxy-modified polysiloxane prepolymer has a structure as shown in formula (I):

[0010]

[0011] Among them, R1 is selected from alkyl, aryl or alkenyl; R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R5 and R6 are independently selected from methyl or phenyl; X is selected from silicone segment, alkyl, aryl, methoxy or ethoxy; m is selected from 0 to 5000, and n is selected from 5 to 25000.

[0012] In some specific embodiments, the polyether-modified isocyanate crosslinking agent has a structure as shown in formula (II):

[0013]

[0014] Wherein, R7 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkyl or aryl; p is selected from 1 to 4; o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r.

[0015] The present invention also provides a method for preparing the aforementioned fouling resistance-releasing coating composition, which comprises:

[0016] The epoxy-modified polysiloxane prepolymer, the wetting and dispersing agent, the anti-settling agent, the pigment and filler, the antifouling agent, the silicone oil and the solvent are uniformly mixed to form a first component;

[0017] The polyether-modified isocyanate cross-linking agent and the solvent are uniformly mixed to form a second component;

[0018] And, the first component and the second component are mixed evenly to prepare a fouling resistance-release coating composition.

[0019] The embodiment of the present invention also provides a polyurethane epoxy modified silicone hydrogel fouling resistance-release coating formed by the aforementioned fouling resistance-release coating composition, wherein the resin in the coating comprises a polyurethane epoxy modified silicone hydrogel antifouling resin.

[0020] An embodiment of the present invention also provides a method for preparing the aforementioned polyurethane epoxy modified silicone hydrogel fouling resistance-release coating, which comprises: uniformly mixing the first component and the second component of the aforementioned fouling resistance-release coating composition to form a mixture, and then applying the mixture to the surface of a substrate and reacting to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0021] The embodiment of the present invention also provides a method for constructing a polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating on a substrate surface, which comprises:

[0022] Applying a tie layer composition at least once on the surface of the substrate to form a tie layer;

[0023] The first component and the second component of the aforementioned fouling resistance-release coating composition are mixed evenly, and applied to the surface of the tie layer for reaction to obtain a polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0024] The embodiments of the present invention also provide the use of the aforementioned fouling resistance-release coating composition or polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating in the field of antifouling engineering in marine environments.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) Compared with existing organosilicon coatings and organosilicon hydrogel coatings, the fouling resistance-releasing coating composition and coating prepared by the present invention contain a large number of hydroxyl groups and amine ester groups. These polar groups can effectively improve their own mechanical strength, adhesion to the substrate, and environmental adaptability of the coating;

[0027] (2) In the present invention, since the active reaction group of the first component is a hydroxyl group / or a part of the residual amino group, and the active reaction group of the second component is an isocyanate group, after the first component and the second component are mixed, the curing and crosslinking method is the chemical crosslinking between the hydroxyl group / or the amino group and the isocyanate group, while the existing organic silicone hydrogel curing and crosslinking method is mainly the hydrolysis and decompression method of silane. The method adopted by the present invention has the advantages of higher reaction activity, low temperature curing, high humidity environment curing, and easy adjustment of curing time, which can effectively avoid the construction difficulties encountered by traditional organic silicone / organic silicone hydrogel antifouling coatings;

[0028] (3) The polyurethane epoxy modified silicone hydrogel fouling resistance-release coating prepared in the present invention has excellent synergistic antifouling ability and more stable surface properties. The internal hydrophilic chain segments can form a hydration layer on the coating surface in an aqueous environment, thereby forming a biological adhesion barrier to hinder the adhesion of foulants; the surface energy and low elastic modulus characteristics of the silicone resin reduce the biological desorption barrier, and even after the organisms adhere to the coating surface, they can be desorbed at a lower water flow rate; the antifouling agent contained in the coating can also be uniformly released to the surrounding area of ​​the coating during the degradation process of the coating, and the hydrophilic layer has the ability to enrich the antifouling agent, thereby fully and efficiently utilizing the biocidal ability of the antifouling agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0030] Figure 1 is an infrared spectrum of the amino-modified polysiloxane prepolymer in Example 1 of the present invention;

[0031] Figure 2is a nuclear magnetic resonance spectrum of the amino-modified polysiloxane prepolymer in Example 1 of the present invention;

[0032] Figure 3 is an infrared spectrum of the epoxy-modified polysiloxane prepolymer in Example 1 of the present invention;

[0033] Figure 4 is an infrared spectrum of the polyether-modified isocyanate cross-linking agent in Example 1 of the present invention;

[0034] Figure 5 is a comparison chart of the number of Escherichia coli adhered to the coating surface in Examples 7-13 of the present invention and Comparative Examples 1-5;

[0035] Figure 6 The comparison diagram of the amount of Chlorella adhered to the coating surface in Examples 7-13 of the present invention and Comparative Examples 1-5 is as follows: Figure 2 shown. DETAILED DESCRIPTION

[0036] In view of the defects of the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Specifically, as one aspect of the technical solution of the present invention, a fouling resistance-release coating composition is involved, comprising a first component and a second component; wherein the first component comprises an epoxy-modified polysiloxane prepolymer, and the second component comprises a polyether-modified isocyanate crosslinker.

[0038] In some preferred embodiments, the epoxy-modified polysiloxane prepolymer has a structure as shown in formula (I):

[0039]

[0040] Among them, R1 is selected from alkyl, aryl or alkenyl; R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R5 and R6 are independently selected from methyl or phenyl; X is selected from silicone segment, alkyl, aryl, methoxy or ethoxy; m is selected from 0 to 5000, and n is selected from 5 to 25000.

[0041] In some preferred embodiments, the polyether-modified isocyanate crosslinking agent has a structure as shown in formula (II):

[0042]

[0043] Wherein, R7 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkyl or aryl; p is selected from 1 to 4; o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r.

[0044] In some preferred embodiments, the method for preparing the epoxy-modified polysiloxane prepolymer comprises:

[0045] A first mixed reaction system comprising hydroxy silicone oil, amino silicate, silicate and a first catalyst is subjected to a decondensation reaction to obtain an amino-modified polysiloxane prepolymer;

[0046] And, the amino-modified polysiloxane prepolymer is subjected to an epoxy ring-opening reaction with an epoxy monomer to obtain an epoxy-modified polysiloxane prepolymer.

[0047] Further, the hydroxy silicone oil includes methyl hydroxy silicone oil and / or phenyl hydroxy silicone oil, but is not limited thereto.

[0048] Furthermore, the hydroxy silicone oil has a structure as shown in formula (III):

[0049]

[0050] Wherein, R5 and R6 are independently selected from methyl or phenyl, and n is selected from 5 to 25000.

[0051] Further, the amino-containing silicate includes any one or more combinations of (3-aminopropyl)ethyldiethoxysilane, 4-anilinotriethoxysilane, 3-aminopropyltriethoxysilane, and N-aminoethyl-3-aminopropyltriethoxysilane, but is not limited thereto.

[0052] Furthermore, the amino-containing silicate has a structure as shown in formula (IV):

[0053]

[0054] Wherein, R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R 11 is selected from alkyl, aryl or alkenyl.

[0055] Further, the silicate includes a difunctional silicate monomer and / or a multifunctional silicate monomer; wherein the difunctional silicate monomer includes dimethoxydimethylsilane and / or diethoxydimethylsilane; the multifunctional silicate monomer includes ethyl orthosilicate and / or trimethoxymethylsilane, and is not limited thereto.

[0056] Furthermore, the silicate has a structure as shown in formula (V):

[0057]

[0058] wherein R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R 11 is selected from alkyl, aryl or alkenyl.

[0059] Further, the first catalyst includes dibutyltin dilaurate, but is not limited thereto.

[0060] Furthermore, the amino-modified polysiloxane prepolymer has a structure as shown in formula (VI):

[0061]

[0062] Among them, R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R5 and R6 are independently selected from methyl or phenyl; X is selected from silicone segment, alkyl, aryl, methoxy or ethoxy; m is selected from 0 to 5000, and n is selected from 5 to 25000.

[0063] Furthermore, the epoxy monomer has a structure as shown in formula (VII):

[0064]

[0065] Wherein, R1 is selected from alkyl, aryl or alkenyl.

[0066] Furthermore, the decondensation reaction is carried out under stirring conditions, and the stirring rate adopted is 400-1000r / min.

[0067] Furthermore, the reaction temperature of the decondensation reaction is 80-130°C.

[0068] Furthermore, the reaction time of the decondensation reaction is 4-24h.

[0069] Furthermore, in a protective atmosphere, under the condition of a stirring speed of 400-1000 r / min, the amino-modified polysiloxane prepolymer is slowly added to the epoxy monomer at 10-40° C. to carry out an epoxy ring-opening reaction.

[0070] Furthermore, the reaction temperature of the epoxy ring-opening reaction is 40-100°C.

[0071] Furthermore, the reaction time of the epoxy ring-opening reaction is 4-48h.

[0072] Furthermore, the mass ratio of the hydroxy silicone oil to the amino group is 100-50:100-20:50-0.01:1-0.01.

[0073] Furthermore, the mass ratio of the amino-modified polysiloxane prepolymer to the epoxy monomer is 100-40:50-3.

[0074] In some more specific embodiments, the method for preparing the epoxy-modified polysiloxane prepolymer comprises:

[0075] (1) Preparation of amino-modified polysiloxane prepolymer: Hydroxyl silicone oil, amino-containing silicate, silicate and the first catalyst are mixed and subjected to decondensation reaction at a reaction temperature of 80-130° C., a stirring time of 4-24 h, and a stirring speed of 400-1000 r / min. After removing the small molecular substances produced by the reaction, an amino-modified polysiloxane prepolymer is prepared. The chemical reaction process is shown in the following formula:

[0076]

[0077] (2) Preparation of epoxy-modified polysiloxane prepolymer: The amino-modified polysiloxane prepolymer is mixed with the epoxy monomer to carry out epoxy ring-opening reaction, the stirring and adding temperature is 10-40° C., the reaction temperature is 40-100° C., the reaction time is 4-48 h, and the stirring speed is 400-1000 r / min. After the reaction is fully completed, the epoxy-modified polysiloxane prepolymer is obtained. The chemical reaction process is shown in the following formula:

[0078]

[0079] Among them, R1 is selected from alkyl, aryl or alkenyl; R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R5 and R6 are independently selected from methyl or phenyl; X is selected from silicone segment, alkyl, aryl, methoxy or ethoxy; m is selected from 0 to 5000, and n is selected from 5 to 25000.

[0080] Furthermore, the adding method in step (2) is to slowly drop the amino-modified polysiloxane prepolymer solution into the epoxy solution.

[0081] In some preferred embodiments, the preparation method of the polyether-modified isocyanate crosslinking agent comprises: subjecting polyether to addition reaction with isocyanate to obtain the polyether-modified isocyanate crosslinking agent; wherein the polyether comprises hydroxyl- and / or amine-terminated polyether.

[0082] Furthermore, the hydrophilic segment in the hydroxyl- and / or amine-terminated polyether is derived from any one or more combinations of polyethylene oxide, polypropylene glycol, polypropylene oxide, and polytetrahydrofuran, but is not limited thereto.

[0083] Furthermore, the hydroxyl and / or amine terminated polyether has a structure as shown in formula (VIII):

[0084]

[0085] Among them, R 13 is selected from alkyl or aryl; R 14 It is selected from hydroxyl or amino; p is selected from 1 to 4; o is selected from 1 to 25000.

[0086] Further, the isocyanate includes HDI trimer curing agent, but is not limited thereto.

[0087] Furthermore, the isocyanate has a structure as shown in formula (IX):

[0088]

[0089] Wherein, R7 is selected from alkyl, aryl or alkenyl, and q is selected from 3 to 7.

[0090] Further, the polyether is slowly added to the isocyanate at 0-50° C. to carry out an addition reaction.

[0091] Furthermore, the reaction temperature of the addition reaction is 40-90°C.

[0092] Furthermore, the reaction time of the addition reaction is 1-24h.

[0093] Furthermore, the mass ratio of the polyether to the isocyanate is 10-1:5-1.

[0094] In some more specific embodiments, the method for preparing the polyether-modified isocyanate crosslinking agent comprises:

[0095] Slowly add isocyanate monomer to the monofunctional polyether hydrophilic segment solution, the temperature when adding the raw materials is 0-50°C, after the raw materials are added, the reaction temperature is adjusted to 40-90°C, the reaction time is 1-24h, and the hydroxyl and / or amine-terminated polyether and isocyanate are subjected to addition reaction to obtain a polyether-modified isocyanate crosslinking agent, and the chemical reaction process is shown in the following formula:

[0096]

[0097] Wherein, R7 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkyl or aryl; R 14 It is selected from hydroxyl or amino; p is selected from 1 to 4; o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r.

[0098] Furthermore, the adding method is to slowly drop the hydroxyl and / or amine terminated polyether solution into the isocyanate solution.

[0099] In some preferred embodiments, the first component further comprises a wetting and dispersing agent, an anti-settling agent, a pigment, a filler, an anti-fouling agent, silicone oil, and a solvent.

[0100] In some preferred embodiments, the second component further comprises a solvent.

[0101] Furthermore, the first component includes the following components calculated in parts by weight: 30-60 parts of epoxy-modified silicone prepolymer, 0.5-3 parts of wetting and dispersing agent, 0.5-4 parts of anti-settling agent, 12-45 parts of pigments and fillers, 5-45 parts of solvents, 0-30 parts of antifouling agent, and 0-30 parts of silicone oil.

[0102] Furthermore, the second component includes the following components calculated in parts by weight: 60-95 parts of a polyether-modified isocyanate crosslinking agent and 40-5 parts of a solvent.

[0103] Furthermore, the mass ratio of the first component to the second component is 10-1:1.

[0104] Furthermore, the NDJ-4 rotational viscosity of the first component is 0.5-7.0 Pa.S.

[0105] Furthermore, the coating-4 cup viscosity of the second component is 30-120s.

[0106] Furthermore, the coating-4 cup viscosity of the second component is 30-70s.

[0107] Furthermore, the anti-settling agent includes any one or more combinations of fumed silica, organic bentonite, and polyamide wax powder, but is not limited thereto.

[0108] Furthermore, the pigment filler includes any one or more combinations of red iron oxide, titanium dioxide, carbon black, mica powder, barium sulfate, talc, and silica powder, but is not limited thereto.

[0109] Further, the wetting and dispersing agent includes any one or more combinations of ANTI-TERRA-U, RG-5172, Disponer923S, and Disponer-110, but is not limited thereto.

[0110] Further, the antifouling agent includes copper pyridine sulfate and / or medetomidine antifouling agent, but is not limited thereto.

[0111] Further, the silicone oil includes methyl-terminated dimethyl silicone oil, but is not limited thereto.

[0112] Further, the solvent includes xylene, but is not limited thereto.

[0113] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned fouling resistance-releasing coating composition, which comprises:

[0114] The epoxy-modified polysiloxane prepolymer, the wetting and dispersing agent, the anti-settling agent, the pigment and filler, the antifouling agent, the silicone oil and the solvent are uniformly mixed to form a first component;

[0115] The polyether-modified isocyanate cross-linking agent and the solvent are uniformly mixed to form a second component;

[0116] And, the first component and the second component are mixed evenly to prepare a fouling resistance-release coating composition.

[0117] Another aspect of the embodiments of the present invention further provides a polyurethane epoxy modified silicone hydrogel fouling resistance-release coating formed by the aforementioned fouling resistance-release coating composition, wherein the resin in the coating comprises a polyurethane epoxy modified silicone hydrogel antifouling resin.

[0118] In some preferred embodiments, the polyurethane epoxy-modified silicone hydrogel antifouling resin has a structure as shown in formula (X):

[0119]

[0120] wherein R1 is selected from an alkyl group, an aryl group or an alkenyl group; R2 is selected from an alkyl group; R3 is selected from a methyl group, a phenyl group or an alkoxy group; R4 is selected from an alkyl group, an aryl group, a methoxy group or an ethoxy group; R5 and R6 are independently selected from a methyl group or a phenyl group; R7 is selected from an alkyl group, an aryl group or an alkenyl group; X is selected from an organosilicon segment, an alkyl group, an aryl group, a methoxy group or an ethoxy group; R 11 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkylaryl; p is selected from 1 to 4, m is selected from 0 to 5000, n is selected from 5 to 25000, o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r.

[0121] Furthermore, the polyurethane epoxy-modified silicone hydrogel antifouling resin is mainly prepared by reacting an epoxy-modified silicone prepolymer with a polyether-modified isocyanate crosslinking agent, and specifically comprises:

[0122] After the epoxy-modified silicone prepolymer in the first component and the polyether-modified isocyanate crosslinker in the second component are mixed, a polyurethane forming reaction is carried out, the ambient temperature is -10-50°C, the reaction time is 15min-24h, and after the reaction is completed, a polyurethane epoxy-modified silicone hydrogel antifouling resin is obtained. The reaction of the polyether-modified isocyanate crosslinker and the epoxy-modified polysiloxane prepolymer is shown in the following formula:

[0123]

[0124] wherein R1 is selected from an alkyl group, an aryl group or an alkenyl group; R2 is selected from an alkyl group; R3 is selected from a methyl group, a phenyl group or an alkoxy group; R4 is selected from an alkyl group, an aryl group, a methoxy group or an ethoxy group; R5 and R6 are independently selected from a methyl group or a phenyl group; R7 is selected from an alkyl group, an aryl group or an alkenyl group; X is selected from an organosilicon segment, an alkyl group, an aryl group, a methoxy group or an ethoxy group; R 11 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkylaryl; p is selected from 1 to 4, m is selected from 0 to 5000, n is selected from 5 to 25000, o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r.

[0125] In some preferred embodiments, the content of the polyether hydrophilic segment in the polyurethane epoxy-modified silicone hydrogel antifouling resin is less than 35%.

[0126] Furthermore, the content of the polyether hydrophilic segment in the polyurethane epoxy-modified silicone hydrogel antifouling resin is 5 to 25 wt %.

[0127] In some preferred embodiments, the content of the silicone resin segment in the polyurethane epoxy-modified silicone hydrogel antifouling resin is 40 to 80 wt %.

[0128] In some preferred embodiments, the content of epoxy segments in the polyurethane epoxy-modified silicone hydrogel antifouling resin is 3 to 20 wt %.

[0129] In some preferred embodiments, the content of the polyurethane segment in the polyurethane epoxy-modified silicone hydrogel antifouling resin is 3 to 20 wt %.

[0130] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned polyurethane epoxy modified silicone hydrogel fouling resistance-release coating, which comprises:

[0131] The first component and the second component of the aforementioned fouling resistance-release coating composition are uniformly mixed to form a mixture, and then the mixture is applied to the surface of a substrate and reacted to obtain the polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating.

[0132] In some preferred embodiments, the NDJ-4 rotational viscosity of the mixture is 0.5-5.5 Pa.S, and the solid content of the mixture is above 55 wt%.

[0133] In some preferred embodiments, the ambient temperature when the mixture is applied to the substrate surface for reaction is -10-50°C.

[0134] In some preferred embodiments, the reaction time when the mixture is applied to the surface of the substrate is 15 minutes to 24 hours.

[0135] In some preferred embodiments, the substrate comprises a low surface energy primer, a silicone primer.

[0136] Another aspect of the embodiments of the present invention further provides a method for constructing a polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating on a substrate surface, comprising:

[0137] Applying a tie layer composition at least once on the surface of the substrate to form a tie layer;

[0138] The first component and the second component of the aforementioned fouling resistance-release coating composition are mixed evenly, and applied to the surface of the tie layer for reaction to obtain a polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0139] In some preferred embodiments, the tie layer composition comprises a tie coat composition and / or a silicone-based primer composition;

[0140] In some preferred embodiments, the mixture of the first component and the second component is coated on the surface of the tie layer 1-3 times by coating; wherein the dry film thickness of a single coat is above 100 μm.

[0141] In some preferred embodiments, the tie layer substrate comprises SeaLion Tiecoat silicone low surface energy tie coat.

[0142] The fouling resistance-releasing coating composition and the polyurethane epoxy-modified silicone hydrogel fouling resistance-releasing coating provided by the present invention have excellent dynamic / static antifouling capabilities. Meanwhile, the coating composition has a simple construction method and has application prospects in the field of marine antifouling engineering.

[0143] The present invention discloses a fouling resistance-releasing coating composition and construction method, which is intended to solve the above-mentioned bottleneck problems currently faced by silicone hydrogel antifouling coatings by combining the structural characteristics of polyurethane resins and epoxy resins. The reaction activity of isocyanates and hydroxyl / amino groups in the coating components can be used to solve the shortcomings of slow drying speed and high construction environment requirements of silicone hydrogel resins; the carbamate groups, hydroxyl groups and imine groups in the polyurethane epoxy modified silicone hydrogel can form hydrogen bonds with each other and with polar functional groups on the surface of the substrate, which can improve the poor strength of the silicone hydrogel antifouling coating itself and the adhesion to the substrate. The hydrophilic segments on the side chains can form a hydration layer on the coating surface, which can increase the difficulty of biological attachment. The high elasticity and low surface energy of the silicone polymer main chain give the coating a low adhesion surface feature. Even if there is biological adhesion, it can be easily desorbed under the shear action of water flow. In addition, the coating composition may also contain a small amount of antifouling agent to kill or repel stubborn attached organisms. The polar functional groups in the hydrophilic chain segment have an enrichment and sustained release effect on certain specific antifouling agents, and can also improve the use efficiency of the antifouling agent.

[0144] Another aspect of the embodiments of the present invention further provides the use of the aforementioned fouling resistance-release coating composition or polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating in the field of antifouling engineering in a marine environment.

[0145] Note 1: When preparing amino-terminated polysiloxane prepolymer, it is preferred to add an appropriate amount of multifunctional siloxane monomers for decondensation reaction, such as trimethoxymethylsilane and tetraethoxysilane, and the reaction product is a dendritic structure or a slightly cross-linked network structure. On the one hand, this structure is conducive to the rapid cross-linking and curing of the coating to form a film after the first component and the second component are mixed, and on the other hand, this structure is conducive to improving the mechanical strength of the resin coating.

[0146] Note 2: When preparing amino-terminated polysiloxane prepolymer, attention should be paid to the changes in the reaction degree and system viscosity. When the separated small molecule product reaches more than 96% of the theoretical yield or the system viscosity increases significantly, the reaction should be stopped immediately. When the system viscosity or reaction degree is too high, it indicates that the prepolymer structure has formed a three-dimensional network structure with a high degree of cross-linking. This structure is not conducive to the subsequent reaction with the second component and the coating film formation process, and reduces the coating performance.

[0147] Note 3: In the chemical reaction process of the addition reaction of the multifunctional isocyanate monomer and the monofunctional polyether hydrophilic chain segment to generate the polyether modified isocyanate crosslinker, the molar ratio (functional group) of the multifunctional isocyanate monomer to the monofunctional polyether hydrophilic chain segment should be controlled between 2 and 4: 0.5 and 2 to ensure that the polyether modified isocyanate crosslinker obtained after the reaction has a sufficient number of isocyanate groups remaining.

[0148] Note 4: In the preparation technology of polyurethane epoxy modified silicone hydrogel involved in the present invention, the proportion of hydrophilic segments in the resin system should be less than 35wt%, preferably in the range of 5wt%-25wt%. Its key role is: on the one hand, too low hydrophilic segment content is not conducive to the formation of hydrogel hydration layer on the coating surface, thereby reducing the resistance to fouling organisms and the slow release capacity of metal ions; on the other hand, too high hydrophilic segment content causes the coating to absorb a large amount of water, which easily leads to insufficient mechanical strength of the coating and a large amount of internal antifouling agent release.

[0149] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0150] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0151] Example 1 (Comb-type amino-modified polysiloxane prepolymer 750-dihydroxyl terminated, isocyanate=2)

[0152] Preparation of polyurethane epoxy modified silicone hydrogel prepolymer

[0153] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 100 parts of hydroxy silicone oil with a molecular weight of about 750, 40 parts of (3-aminopropyl)ethyldiethoxysilane, 10 parts of diethoxydimethylsilane and 2 to 3 drops of dibutyltin dilaurate are fully mixed and added to a 1000 ml reaction bottle. The temperature is raised to 110°C at a speed of 600 r / min and the stirring reaction is continued for 8 hours. During the reaction, the small molecular substances generated by the reaction are separated from the reaction bottle by vacuum evaporation. As the reaction proceeds, the viscosity of the reactants gradually increases. After the reaction is completed, the temperature is lowered to room temperature to obtain an amino-modified polysiloxane prepolymer; wherein, the infrared spectrum of the amino-modified polysiloxane prepolymer is shown in the figure Figure 1 The NMR spectrum is shown in Figure 2 shown.

[0154] (2) Preparation of epoxy-modified polysiloxane prepolymer in the first component: Add 150 parts of amino-modified polysiloxane prepolymer and 50 parts of toluene into a reaction bottle, stir at a speed of 600 r / min, and introduce nitrogen into it. At room temperature, slowly drip 40 parts of glycidyl ether into the reaction bottle. After the addition is completed, heat to 60°C and react for 12 hours. After the epoxy ring-opening reaction is completed, cool to room temperature to obtain a viscous epoxy-modified polysiloxane prepolymer. Seal it to avoid light and let it stand for use; the infrared spectrum of the epoxy-modified polysiloxane prepolymer is as shown in the figure. Figure 3 shown.

[0155] (3) Preparation of polyether-modified isocyanate crosslinker in the second component: Add 100 parts of HDI trimer curing agent and 50 parts of toluene into a reaction bottle, stir at a speed of 600 r / min, and introduce nitrogen into it. At room temperature, slowly drip 100 parts of polyethylene glycol monomethyl ether (500 molecular weight) into the reaction bottle, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is completed, heat to 60°C and react for 24 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyether-modified isocyanate crosslinker. Seal it to avoid light and set it aside for use; the infrared spectrum of the polyether-modified isocyanate crosslinker is as shown in the figure Figure 4 shown.

[0156] Example 2 (Comb-type amino-modified polysiloxane prepolymer 500-monohydroxyl terminated, isocyanate=2)

[0157] Preparation of polyurethane epoxy modified silicone hydrogel prepolymer

[0158] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 100 parts of hydroxy silicone oil with a molecular weight of about 500, 40 parts of 3-aminopropylethyldiethoxysilane, 10 parts of diethoxydimethylsilane and 2 to 3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 120°C at 800 r / min, and stirred for 6 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0159] (2) Preparation of epoxy-modified polysiloxane prepolymer in the first component: 150 parts of amino-modified polysiloxane prepolymer and 50 parts of toluene were added to a reaction bottle, stirred at 800 r / min, and nitrogen was introduced therein. 40 parts of 1,2-butylene oxide were slowly dripped into the reaction bottle at room temperature. After the addition was completed, the temperature was raised to 80°C and the reaction was carried out for 8 hours. After the epoxy ring-opening reaction was completed, the temperature was lowered to room temperature to obtain a viscous epoxy-modified polysiloxane prepolymer, which was sealed to avoid light and left to stand for use.

[0160] (3) Preparation of polyether-modified isocyanate crosslinker in the second component: Add 100 parts of HDI trimer curing agent and 100 parts of toluene to a reaction bottle, stir at 800 r / min, and introduce nitrogen. At room temperature, slowly drip 100 parts of polyethylene glycol monomethyl ether (1000 molecular weight) into the reaction bottle, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is completed, heat to 80°C and react for 8 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyether-modified isocyanate crosslinker, seal it to avoid light, and let it stand for use.

[0161] Example 3 (Comb-shaped amino-modified polysiloxane prepolymer-dihydroxyl and amino residual end-capping, isocyanate>2)

[0162] Preparation of polyurethane epoxy modified silicone hydrogel prepolymer

[0163] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 100 parts of hydroxy silicone oil with a molecular weight of about 750, 50 parts of (3-aminopropyl) ethyl diethoxysilane and 2 to 3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 100°C at a speed of 400 r / min, and stirred for 12 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0164] (2) Preparation of epoxy-modified polysiloxane prepolymer in the first component: 150 parts of amino-modified polysiloxane prepolymer and 40 parts of toluene were added to a reaction bottle, stirred at 400 r / min, and nitrogen was introduced. 40 parts of glycidyl ether were slowly dripped into the reaction bottle at room temperature. After the addition was completed, the temperature was raised to 70°C and the reaction was allowed to react for 18 hours. After the epoxy ring-opening reaction was completed, the temperature was lowered to room temperature to obtain a viscous epoxy-modified polysiloxane prepolymer, which was sealed and kept away from light and allowed to stand for use.

[0165] (3) Preparation of polyether-modified isocyanate crosslinker in the second component: Add 100 parts of HDI trimer curing agent and 40 parts of toluene to a reaction bottle, stir at 400 r / min, and introduce nitrogen. At room temperature, slowly drip 80 parts of amino-terminated polyethylene glycol monomethyl ether (500 molecular weight) into the reaction bottle, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 50°C and react for 24 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyether-modified isocyanate crosslinker, seal it to avoid light, and let it stand for use.

[0166] Example 4 (Micro-crosslinked amino-modified polysiloxane prepolymer-monohydroxyl terminated, isocyanate <2)

[0167] Preparation of polyurethane epoxy modified silicone hydrogel prepolymer

[0168] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 100 parts of hydroxy silicone oil with a molecular weight of about 750, 30 parts of 3-aminopropyltriethoxysilane, and 2 to 3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 90°C at a speed of 1000 r / min, and stirred for 24 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0169] (2) Preparation of epoxy-modified polysiloxane prepolymer in the first component: 140 parts of amino-modified polysiloxane prepolymer and 60 parts of toluene were added to a reaction bottle, stirred at a speed of 1000 r / min, and nitrogen was introduced therein. 30 parts of phenyl glycidyl ether were slowly dripped into the reaction bottle at room temperature. After the addition was completed, the temperature was raised to 90°C and the reaction was carried out for 10 hours. After the epoxy ring-opening reaction was completed, the temperature was lowered to room temperature to obtain a viscous epoxy-modified polysiloxane prepolymer, which was sealed and protected from light and left to stand for use.

[0170] (3) Preparation of polyether-modified isocyanate crosslinker in the second component: Add 100 parts of HDI trimer curing agent and 60 parts of toluene to a reaction bottle, stir at 1000 r / min, and introduce nitrogen. At room temperature, slowly drip 120 parts of amino-terminated polyethylene glycol monomethyl ether (350 molecular weight) into the reaction bottle, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 70°C and react for 16 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyether-modified isocyanate crosslinker, seal it to avoid light, and let it stand for use.

[0171] Example 5 (Micro-crosslinked amino-modified polysiloxane prepolymer-segment compounding-dihydroxyl and amino residual end-capping, isocyanate=2)

[0172] Preparation of polyurethane epoxy modified silicone hydrogel prepolymer

[0173] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 50 parts of hydroxy silicone oil with a molecular weight of about 500, 50 parts of hydroxy silicone oil with a molecular weight of about 2000, 40 parts of 3-aminopropyltriethoxysilane, and 2 to 3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 130°C at 700 r / min, and stirred for 5 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0174] (2) Preparation of epoxy-modified polysiloxane prepolymer in the first component: 150 parts of amino-modified polysiloxane prepolymer and 40 parts of toluene were added to a reaction bottle, stirred at 700 r / min, and nitrogen was introduced. 30 parts of glycidyl ether were slowly dripped into the reaction bottle at room temperature. After the addition was completed, the temperature was raised to 60°C and the reaction was carried out for 16 hours. After the epoxy ring-opening reaction was completed, the temperature was lowered to room temperature to obtain a viscous epoxy-modified polysiloxane prepolymer, which was sealed and kept away from light and allowed to stand for use.

[0175] (3) Preparation of polyether-modified isocyanate crosslinker in the second component: Add 100 parts of HDI trimer curing agent and 60 parts of toluene to a reaction bottle, stir at 700 r / min, and introduce nitrogen. At room temperature, slowly drip 100 parts of polyethylene glycol monomethyl ether (50 parts of 350 molecular weight and 2000 molecular weight, evenly mixed) into the reaction bottle, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 40°C and react for 48 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyether-modified isocyanate crosslinker, seal it to avoid light, and let it stand for use.

[0176] Example 6 (amino-modified polysiloxane prepolymer with linear amino-terminated structure-chain segment compounding-diepoxy ring opening, isocyanate=2)

[0177] Preparation of polyurethane epoxy modified silicone hydrogel prepolymer

[0178] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 100 parts of hydroxy silicone oil (25 parts of each hydroxy silicone oil with a molecular weight of 500 / 750 / 2000 / 4200), 50 parts of 3-aminopropyldimethylethoxysilane and 2-3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 110°C at a speed of 500 r / min, and stirred for 10 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0179] (2) Preparation of epoxy-modified polysiloxane prepolymer in the first component: 150 parts of amino-modified polysiloxane prepolymer and 100 parts of toluene were added to a reaction bottle, stirred at a speed of 500 r / min, and nitrogen was introduced therein. At room temperature, 20 parts of bisphenol A diglycidyl ether were slowly dripped into the reaction bottle. After the addition was completed, the temperature was raised to 70°C and the reaction was carried out for 24 hours. After the epoxy ring-opening reaction was completed, the temperature was lowered to room temperature to obtain a viscous epoxy-modified polysiloxane prepolymer, which was sealed to avoid light and left to stand for use.

[0180] (3) Preparation of polyether-modified isocyanate crosslinker in the second component: Add 100 parts of triphenyl isocyanate thiophosphate curing agent and 70 parts of toluene to a reaction bottle, stir at 500 r / min, and introduce nitrogen. Slowly drip 100 parts of polyethylene glycol monomethyl ether (500 molecular weight and 100 molecular weight polyethylene glycol monomethyl ether, 50 parts each, uniformly mixed) into the reaction bottle at room temperature, always pay attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 85°C and react for 8 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyether-modified isocyanate crosslinker, seal and avoid light, and stand for use.

[0181] Example 7 (Using the epoxy-modified polysiloxane prepolymer and polyether-modified isocyanate crosslinking agent prepared in Example 1)

[0182] Preparation of polyurethane epoxy modified silicone hydrogel antifouling coating composition

[0183] In this embodiment, the polyurethane epoxy-modified silicone hydrogel antifouling coating includes a first component and a second component, wherein the first component includes an epoxy-modified polysiloxane prepolymer, and the second component includes a polyether-modified isocyanate crosslinking agent. Each component is made of the following ingredients based on a total weight of 100 parts:

[0184] Preparation of the first component, amino-modified polysiloxane prepolymer resin: 40 parts of the epoxy-modified polysiloxane prepolymer obtained in Example 1, 5 parts of silicone oil with a viscosity of 500±30mPa.s, and 25 parts of xylene are added to a mixing pot and stirred at a speed of 3000r / min for 5 minutes, and then 1 part of ANTI-TERRA-U wetting and dispersing agent and 0.5 part of fumed silica anti-settling agent are added in sequence, and then 7 parts of red iron oxide, 1 part of bentonite, 7 parts of silicon micropowder, 3.5 parts of mica powder, and 10 parts of zinc oxide are added, and stirring is continued at the same speed for 20 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, the viscosity is adjusted to an NDJ-4 rotational viscosity of 2.5Pa.S with xylene, and the first component is obtained by filtering and packaging.

[0185] Preparation of the second component, polyether modified isocyanate crosslinker: Add 90 parts of polyether modified isocyanate crosslinker and 10 parts of xylene into a mixing pot, stir evenly, adjust the viscosity of the mixture to 40S in a T-4 cup with xylene, and filter and package to obtain the second component.

[0186] The first component and the second component are mixed and stirred evenly in a mass ratio of 5:1, and coated on the surface of the substrate to form a film to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0187] Example 8 (Using the epoxy-modified polysiloxane prepolymer and polyether-modified isocyanate crosslinking agent prepared in Example 2)

[0188] Preparation of polyurethane epoxy modified silicone hydrogel antifouling coating composition

[0189] In this embodiment, the polyurethane epoxy modified silicone hydrogel antifouling coating comprises a first component and a second component, wherein the first component comprises an amino modified polysiloxane prepolymer, and the second component comprises a polyether modified isocyanate crosslinking agent. Each component is made of the following ingredients based on a total weight of 100 parts:

[0190] Preparation of the first component, amino-modified polysiloxane prepolymer resin: 45 parts of the epoxy-modified polysiloxane prepolymer obtained in Example 2, 17 parts of xylene and 8 parts of silicone oil with a viscosity of 500±30mPa.s are added to a mixing pot and stirred at a speed of 4000r / min for 5 minutes, and then 2 parts of RG-5172 wetting and dispersing agent, 2 parts of bentonite, and 2 parts of fumed silica anti-settling agent are added in sequence, and then 10 parts of red iron oxide, 4 parts of mica powder, 5 parts of zinc oxide, and 6 parts of titanium dioxide are added, and stirring is continued at the same speed for 20 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, the viscosity is adjusted to NDJ-4 rotational viscosity of 3.5Pa.S with xylene, and the first component is obtained by filtering and packaging.

[0191] Preparation of the second component, polyether modified isocyanate crosslinker: Add 95 parts of polyether modified isocyanate crosslinker and 5 parts of xylene into a mixing pot, stir evenly, adjust the viscosity of the mixture to 30S in a T-4 cup with xylene, and filter and package to obtain the second component.

[0192] The first component and the second component are mixed and stirred evenly in a mass ratio of 6:1, and coated on the surface of the substrate to form a film to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0193] Example 9 (Using the epoxy-modified polysiloxane prepolymer and polyether-modified isocyanate crosslinking agent prepared in Example 3)

[0194] Preparation of polyurethane epoxy modified silicone hydrogel antifouling coating composition

[0195] In this embodiment, the polyurethane epoxy-modified silicone hydrogel antifouling coating includes a first component and a second component, wherein the first component includes an epoxy-modified polysiloxane prepolymer, and the second component includes a polyether-modified isocyanate crosslinking agent. Each component is made of the following ingredients based on a total weight of 100 parts:

[0196] Preparation of the first component, amino-modified polysiloxane prepolymer resin: 35 parts of the epoxy-modified polysiloxane prepolymer obtained in Example 3, 19 parts of xylene and 6 parts of silicone oil with a viscosity of 500±30mPa.s are added to a mixing pot and stirred at a speed of 7000r / min for 5min, and then 0.5 parts of RG-5172 wetting and dispersing agent, 0.5 parts of Disponer923S wetting and dispersing agent, 1.5 parts of polyamide wax powder anti-settling agent, and 0.5 parts of fumed silica anti-settling agent are added in sequence, and then 12 parts of red iron oxide, 5 parts of mica powder, 8 parts of silicon micropowder, 7 parts of zinc oxide, and 5 parts of barium sulfate are added, and stirring is continued at the same speed for 20min, and the mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to NDJ-4 rotational viscosity of 4.0Pa.S with xylene, and filtered and packaged to obtain the first component.

[0197] Preparation of the second component, polyether modified isocyanate crosslinker: Add 85 parts of polyether modified isocyanate crosslinker and 15 parts of xylene into a mixing pot, stir evenly, adjust the viscosity of the mixture to 30S in a T-4 cup with xylene, and filter and package to obtain the second component.

[0198] The first component and the second component are mixed and stirred evenly in a mass ratio of 6.5:1, and coated on the surface of the substrate to form a film to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0199] Example 10 (Using the epoxy-modified polysiloxane prepolymer and polyether-modified isocyanate crosslinking agent prepared in Example 4)

[0200] Preparation of polyurethane epoxy modified silicone hydrogel antifouling coating composition

[0201] In this embodiment, the polyurethane epoxy-modified silicone hydrogel antifouling coating includes a first component and a second component, wherein the first component includes an epoxy-modified polysiloxane prepolymer, and the second component includes a polyether-modified isocyanate crosslinking agent. Each component is made of the following ingredients based on a total weight of 100 parts:

[0202] Preparation of the first component, amino-modified polysiloxane prepolymer resin: 30 parts of the epoxy-modified polysiloxane prepolymer obtained in Example 4 and 35 parts of xylene are added to a mixing pot and stirred at a speed of 5000r / min for 5 minutes, and then 0.5 parts of RG-5172 wetting and dispersing agent, 1 part of DISPERBYK-110 wetting and dispersing agent, 0.5 parts of polyamide wax powder anti-settling agent, and 0.5 parts of fumed silica anti-settling agent are added in sequence, and then 2 parts of bentonite, 7 parts of zinc oxide, 5 parts of titanium dioxide, 10 parts of carbon black, 3 parts of barium sulfate, and 6 parts of talc are added, and stirring is continued at the same speed for 20 minutes, and the mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to NDJ-4 rotational viscosity of 2.0Pa.S with xylene. Filter and package to obtain the first component.

[0203] Preparation of the second component, polyether modified isocyanate crosslinker: add 80 parts of polyether modified isocyanate crosslinker and 20 parts of xylene into a mixing pot, stir evenly, adjust the viscosity of the mixture to T-4 cup 50S with xylene, filter and package to obtain the second component.

[0204] The first component and the second component are mixed and stirred evenly in a mass ratio of 9:1, and coated on the surface of the substrate to form a film to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0205] Example 11 (Using the epoxy-modified polysiloxane prepolymer and polyether-modified isocyanate crosslinking agent prepared in Example 5)

[0206] Preparation of polyurethane epoxy modified silicone hydrogel antifouling coating composition

[0207] In this embodiment, the polyurethane epoxy-modified silicone hydrogel antifouling coating includes a first component and a second component, wherein the first component includes an epoxy-modified polysiloxane prepolymer, and the second component includes a polyether-modified isocyanate crosslinking agent. Each component is made of the following ingredients based on a total weight of 100 parts:

[0208] Preparation of the first component, amino-modified polysiloxane prepolymer resin: 50 parts of the epoxy-modified polysiloxane prepolymer obtained in Example 5, 20 parts of xylene and 3 parts of silicone oil with a viscosity of 500±30mPa.s are added to a mixing pot and stirred at a speed of 6000r / min for 5min, and then 0.5 parts of RG-5172 wetting and dispersing agent, 1 part of Disponer904S wetting and dispersing agent, and 1.5 parts of fumed silica anti-settling agent are added in sequence, and then 2.5 parts of bentonite, 2 parts of silicon micropowder, 5 parts of zinc oxide, 8 parts of titanium dioxide, 2 parts of barium sulfate, and 5 parts of talc are added, and stirring is continued at the same speed for 20min, and the mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to NDJ-4 rotational viscosity of 1.5Pa.S with xylene, and filtered and packaged to obtain the first component.

[0209] Preparation of the second component, polyether modified isocyanate crosslinker: Add 85 parts of polyether modified isocyanate crosslinker and 15 parts of xylene into a mixing pot, stir evenly, adjust the viscosity of the mixture to 60S in a T-4 cup with xylene, and filter and package to obtain the second component.

[0210] The first component and the second component are mixed and stirred evenly in a mass ratio of 6:1, and coated on the surface of the substrate to form a film to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0211] Example 12 (Using the epoxy-modified polysiloxane prepolymer and polyether-modified isocyanate crosslinking agent prepared in Example 6)

[0212] Preparation of polyurethane epoxy modified silicone hydrogel antifouling coating composition

[0213] In this embodiment, the polyurethane epoxy-modified silicone hydrogel antifouling coating includes a first component and a second component, wherein the first component includes an epoxy-modified polysiloxane prepolymer, and the second component includes a polyether-modified isocyanate crosslinking agent. Each component is made of the following ingredients based on a total weight of 100 parts:

[0214] Preparation of the first component, amino-modified polysiloxane prepolymer resin: 55 parts of the epoxy-modified polysiloxane prepolymer obtained in Example 6, 10 parts of xylene and 5 parts of silicone oil with a viscosity of 500±30mPa.s are added to a mixing pot and stirred at a speed of 5000r / min for 5min, and then 1 part of Disponer923S wetting and dispersing agent, 1.5 parts of Disponer904S wetting and dispersing agent, 0.5 parts of fumed silica anti-settling agent, 0.5 parts of polyamide wax powder anti-settling agent, and then 0.5 parts of bentonite, 8 parts of red iron oxide, 6 parts of mica powder, 5 parts of silica powder, 2 parts of titanium dioxide, and 5 parts of talc are added. Stirring is continued at the same speed for 20min, and the mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to NDJ-4 rotational viscosity of 3Pa.S with xylene. Filter and package to obtain the first component.

[0215] Preparation of the second component, polyether modified isocyanate crosslinker: Add 95 parts of polyether modified isocyanate crosslinker and 5 parts of xylene into a mixing pot, stir evenly, adjust the viscosity of the mixture to 70S in a T-4 cup with xylene, and obtain the second component after filtering and packaging.

[0216] The first component and the second component are mixed and stirred evenly in a mass ratio of 7:1, and coated on the surface of the substrate to form a film to obtain the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

[0217] Example 13 (using the epoxy-modified polysiloxane prepolymer prepared in Example 1 and the polyether-modified isocyanate cross-linking agent + antifouling agent solution)

[0218] Polyurethane epoxy modified silicone hydrogel antifouling coating composition and coating with additional antifouling agent added

[0219] In this Example 13, amino-modified polysiloxane prepolymer and epoxy-modified polysiloxane prepolymer were prepared by the same formula parts and preparation method as in Example 1; the first component and the second component were prepared by the same method and formula as in Example 7, except that 10 parts of copper pyridine sulfate antifouling agent were additionally added to the first component; the polyurethane epoxy-modified silicone hydrogel antifouling coating composition and coating were prepared by the same method as in Example 7, except that the dosage ratio of the first component to the second component was 5.2:1.

[0220] Comparative Example 1

[0221] Polyurethane epoxy modified organosilicon antifouling coating composition and coating (without hydrogel segment)

[0222] In this comparative example 1, amino-modified polysiloxane prepolymer and epoxy-modified polysiloxane prepolymer are prepared by the same formula parts and preparation method as in Example 1; the first component is prepared by the same method and formula as in Example 7; the second component is prepared by the same method as in Example 7, except that the polyether-modified isocyanate is replaced with an HDI trimer curing agent; the polyurethane epoxy-modified silicone antifouling coating composition and coating are prepared by the same method as in Example 7, except that the dosage ratio of the first component to the second component is 10:1.

[0223] Comparative Example 2

[0224] Polyurethane modified silicone hydrogel antifouling coating composition and coating (without epoxy segment modification)

[0225] In this comparative example 2, the amino-modified polysiloxane prepolymer is prepared by the same formula and preparation method as in Example 2; the first component is prepared by the same method and formula as in Example 8, except that the raw material epoxy-modified organosilicon prepolymer is replaced with an amino-modified polysiloxane prepolymer; the polyurethane-modified organosilicon antifouling coating composition and coating are prepared by the same method as in Example 8, and the ratio of the first component to the second component is 5.5:1. Considering the rapid reaction between isocyanate and amino group, the coating method adopts a two-component spraying method.

[0226] Comparative Example 3

[0227] Epoxy-modified organosilicon antifouling coating composition and coating (without hydrogel segment and polyurethane segment)

[0228] In this comparative example 3, an amino-modified polysiloxane prepolymer is prepared by the same formula parts and preparation method as in Example 3; the first component is prepared by the same method and formula as in Example 9, except that the raw material epoxy-modified silicone prepolymer is replaced by an amino-modified polysiloxane prepolymer; the second component is prepared by the same method as in Example 9, except that the polyether-modified isocyanate is replaced by an epoxy resin prepolymer (E51); the epoxy-modified silicone antifouling coating composition and coating are prepared by the same method as in Example 9, except that the dosage ratio of the first component to the second component is 6:1.

[0229] Comparative Example 4

[0230] Epoxy resin coating compositions and coatings (pure epoxy resin systems)

[0231] In this comparative example 4, the first component is prepared by the same method as in Example 10, except that the epoxy-modified silicone prepolymer in the first component is replaced with epoxy resin E51; the second component is prepared by the same method as in Example 10, except that the polyether-modified isocyanate prepolymer is replaced with epoxy curing agent (T403); the epoxy resin transition layer coating composition and coating are prepared by the same method as in Example 10, except that the dosage ratio of the first component to the second component is 4.5:1.

[0232] Comparative Example 5

[0233] Silicone resin coating composition and coating (pure silicone resin system)

[0234] In this comparative example 5, the first component is prepared by the same method as in Example 11, except that the epoxy-modified silicone prepolymer in the first component is replaced with Dow Corning 184 silicone resin prepolymer; the second component is prepared by the same method as in Example 11, except that the polyether-modified isocyanate prepolymer is replaced with Dow Corning 184 silicone resin crosslinker; the silicone resin transition layer coating composition and coating are prepared by the same method as in Example 11, except that the dosage ratio of the first component to the second component is 15.5:1.

[0235] Test experiment:

[0236] According to the test items, the corresponding test substrates were selected. The contact angle and laboratory antifouling performance tests used carrier sheets as the substrate (thickness: 1mm), the drying time used Q235 steel plates, and the adhesion (pull-off method) test used Q235 steel plates, epoxy composite plates, silicone composite plates and homemade silicone connecting paints as test pieces. Each sample was coated once, and the test was conducted by air spraying, with the dry film thickness controlled at (100±10)μm. The test results are shown in Table 1:

[0237] Table 1 Performance test results of coatings of Examples 7-13 and Comparative Examples 1-5

[0238]

[0239]

[0240] The comparison of the number of Escherichia coli adhered to the coating surface in Examples 7-13 and Comparative Examples 1-5 is shown in the figure below: Figure 5 As shown in the figure, the comparison of the number of attached Chlorella is as follows Figure 6As shown; by comparing Examples 7-13 with Comparative Examples 1-5, it can be seen that the selection of polyurethane segments, epoxy segments and silicone segments and their contents in the antifouling coating (polyurethane epoxy-modified silicone hydrogel antifouling coating resin) plays a very critical role in the substrate adhesion and other properties of the product; the selection and ratio of the multifunctional monomer, crosslinking agent and prepolymer determines the properties of the coating crosslinking density and curing time; the selection and content of the silicone segment, hydrogel segment (polyether segment) and antifouling agent in the antifouling coating plays a very critical role in the contact angle and antibacterial / seaweed adhesion properties of the product.

[0241] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0242] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. A fouling resistance-releasing coating composition, characterized in that: The coating composition comprises a first component and a second component; wherein the first component comprises an epoxy-modified polysiloxane prepolymer, and the second component comprises a polyether-modified isocyanate crosslinking agent.

2. The coating composition according to claim 1, characterized in that: The epoxy-modified polysiloxane prepolymer has a structure as shown in formula (I): Wherein, R1 is selected from alkyl, aryl or alkenyl; R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R5 and R6 are independently selected from methyl or phenyl; X is selected from organosilicon segment, alkyl, aryl, methoxy or ethoxy; m is selected from 0 to 5000, and n is selected from 5 to 25000; And / or, the polyether-modified isocyanate cross-linking agent has a structure as shown in formula (II): Wherein, R7 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkyl or aryl; p is selected from 1 to 4; o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r.

3. The coating composition according to claim 1, characterized in that The preparation method of the epoxy-modified polysiloxane prepolymer comprises: A first mixed reaction system comprising hydroxy silicone oil, amino silicate, silicate and a first catalyst is subjected to a decondensation reaction to obtain an amino-modified polysiloxane prepolymer; And, the amino-modified polysiloxane prepolymer is subjected to an epoxy ring-opening reaction with an epoxy monomer to obtain an epoxy-modified polysiloxane prepolymer.

4. The coating composition according to claim 3, characterized in that The hydroxy silicone oil includes methyl hydroxy silicone oil and / or phenyl hydroxy silicone oil; And / or, the hydroxy silicone oil has a structure as shown in formula (III): Wherein, R5 and R6 are independently selected from methyl or phenyl, and n is selected from 5 to 25000; And / or, the amino-containing silicate comprises any one or more combinations of (3-aminopropyl)ethyldiethoxysilane, 4-anilinotriethoxysilane, 3-aminopropyltriethoxysilane, and N-aminoethyl-3-aminopropyltriethoxysilane; And / or, the amino-containing silicate has a structure as shown in formula (IV): Wherein, R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R 11 is selected from alkyl, aryl or alkenyl; And / or, the silicate includes a difunctional silicate monomer and / or a multifunctional silicate monomer; wherein the difunctional silicate monomer includes dimethoxydimethylsilane and / or diethoxydimethylsilane; the multifunctional silicate monomer includes ethyl orthosilicate and / or trimethoxymethylsilane; And / or, the silicate has a structure as shown in formula (V): wherein R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R 11 is selected from alkyl, aryl or alkenyl; and / or, the first catalyst comprises dibutyltin dilaurate; And / or, the amino-modified polysiloxane prepolymer has a structure as shown in formula (VI): Wherein, R2 is selected from alkyl; R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl, methoxy or ethoxy; R5 and R6 are independently selected from methyl or phenyl; X is selected from organosilicon segment, alkyl, aryl, methoxy or ethoxy; m is selected from 0 to 5000, and n is selected from 5 to 25000; And / or, the epoxy monomer has a structure as shown in formula (VII): Wherein, R1 is selected from alkyl, aryl or alkenyl.

5. The coating composition according to claim 3, characterized in that The decondensation reaction is carried out under stirring conditions, and the stirring rate adopted is 400-1000r / min; and / or, the reaction temperature of the decondensation reaction is 80-130° C.; and / or, the reaction time of the decondensation reaction is 4-24 h; and / or, in a protective atmosphere, slowly adding the amino-modified polysiloxane prepolymer to the epoxy monomer at 10-40° C. at a stirring speed of 400-1000 r / min to carry out an epoxy ring-opening reaction; and / or, the reaction temperature of the epoxy ring-opening reaction is 40-100° C.; and / or, the reaction time of the epoxy ring-opening reaction is 4-48 h; and / or, the mass ratio of the hydroxy silicone oil, the amino-containing silicate, the silicate and the first catalyst is 100-50:100-20:50-0.01:1-0.01; And / or, the mass ratio of the amino-modified polysiloxane prepolymer to the epoxy monomer is 100-40:50-3.

6. The coating composition according to claim 1, characterized in that The preparation method of the polyether-modified isocyanate crosslinking agent comprises: subjecting polyether to addition reaction with isocyanate to obtain the polyether-modified isocyanate crosslinking agent; wherein the polyether comprises hydroxyl- and / or amine-terminated polyether.

7. The coating composition according to claim 6, characterized in that: The hydrophilic segments in the hydroxyl and / or amine-terminated polyether are derived from any one or more combinations of polyethylene oxide, polypropylene glycol, polypropylene oxide, and polytetrahydrofuran; And / or, the hydroxyl and / or amine terminated polyether has a structure as shown in formula (VIII): Among them, R 13 is selected from alkyl or aryl; R 14 hydroxyl or amino; p is selected from 1 to 4; o is selected from 1 to 25000; and / or, the isocyanate comprises an HDI trimer curing agent; And / or, the isocyanate has a structure as shown in formula (IX): Wherein, R7 is selected from alkyl, aryl or alkenyl; q is selected from 3 to 7.

8. The coating composition according to claim 6, characterized in that: Slowly add the polyether to the isocyanate at 0-50°C to carry out addition reaction; and / or, the reaction temperature of the addition reaction is 40-90° C.; and / or, the reaction time of the addition reaction is 1-24 h; And / or, the mass ratio of the polyether to the isocyanate is 10-1:5-1.

9. The coating composition according to claim 1, characterized in that: The first component also includes a wetting and dispersing agent, an anti-settling agent, a pigment and filler, an antifouling agent, silicone oil and a solvent; And / or, the second component further comprises a solvent.

10. The coating composition according to claim 9, characterized in that The first component includes the following components calculated by weight: 30-60 parts of epoxy modified silicone prepolymer, 0.5-3 parts of wetting and dispersing agent, 0.5-4 parts of anti-settling agent, 12-45 parts of pigments and fillers, 5-45 parts of solvents, 0-30 parts of antifouling agent, and 0-30 parts of silicone oil; And / or, the second component comprises the following components calculated in parts by weight: 60-95 parts of a polyether-modified isocyanate crosslinking agent and 40-5 parts of a solvent; and / or, the mass ratio of the first component to the second component is 10-1:1; and / or, the NDJ-4 rotational viscosity of the first component is 0.5-7.0 Pa.S; and / or, the coating-4 cup viscosity of the second component is 30-120s, preferably 30-70s; And / or, the anti-settling agent includes any one or more combinations of fumed silica, organic bentonite, and polyamide wax powder; And / or, the pigment filler includes any one or more combinations of red iron oxide, titanium dioxide, carbon black, mica powder, barium sulfate, talc powder, and silica powder; And / or, the wetting and dispersing agent includes any one or more combinations of ANTI-TERRA-U, RG-5172, Disponer923S, Disponer-110; and / or, the antifouling agent includes copper pyridine sulfate antifouling agent and / or medetomidine; and / or, the silicone oil includes methyl-terminated dimethyl silicone oil; and / or, the solvent includes xylene.

11. A method for preparing a fouling resistance-releasing coating composition according to any one of claims 1 to 10, characterized in that: include: The epoxy-modified polysiloxane prepolymer, the wetting and dispersing agent, the anti-settling agent, the pigment and filler, the antifouling agent, the silicone oil and the solvent are uniformly mixed to form a first component; The polyether-modified isocyanate cross-linking agent and the solvent are uniformly mixed to form a second component; And, the first component and the second component are mixed evenly to prepare a fouling resistance-release coating composition.

12. The polyurethane epoxy modified silicone hydrogel fouling resistance-release coating formed by the fouling resistance-release coating composition according to any one of claims 1 to 10, characterized in that: The resin in the coating layer includes polyurethane epoxy modified organic silicon hydrogel antifouling resin.

13. The polyurethane epoxy modified silicone hydrogel fouling resistance-release coating according to claim 12, characterized in that: The polyurethane epoxy modified silicone hydrogel antifouling resin has a structure as shown in formula (X): wherein R1 is selected from an alkyl group, an aryl group or an alkenyl group; R2 is selected from an alkyl group; R3 is selected from a methyl group, a phenyl group or an alkoxy group; R4 is selected from an alkyl group, an aryl group, a methoxy group or an ethoxy group; R5 and R6 are independently selected from a methyl group or a phenyl group; R7 is selected from an alkyl group, an aryl group or an alkenyl group; X is selected from an organosilicon segment, an alkyl group, an aryl group, a methoxy group or an ethoxy group; R 11 is selected from alkyl, aryl or alkenyl; R 12 is selected from oxygen or imine; R 13 is selected from alkylaryl; p is selected from 1 to 4, m is selected from 0 to 5000, n is selected from 5 to 25000, o is selected from 1 to 25000; r is selected from 1 to 4, q is selected from 3 to 7, and q>r; And / or, the content of the polyether hydrophilic segment in the polyurethane epoxy modified silicone hydrogel antifouling resin is less than 35%; preferably, the content of the polyether hydrophilic segment in the polyurethane epoxy modified silicone hydrogel antifouling resin is 5 to 25wt%; And / or, the content of the silicone resin segment in the polyurethane epoxy modified silicone hydrogel antifouling resin is 40 to 80 wt%; And / or, the content of epoxy segments in the polyurethane epoxy-modified silicone hydrogel antifouling resin is 3 to 20 wt%; And / or, the content of the polyurethane segment in the polyurethane epoxy-modified silicone hydrogel antifouling resin is 3-20wt%.

14. The method for preparing the polyurethane epoxy modified silicone hydrogel fouling resistance-release coating according to claim 12 or 13, characterized in that: include: The first component and the second component of the fouling resistance-release coating composition described in any one of claims 1 to 10 are uniformly mixed to form a mixture, and then the mixture is applied to the surface of a substrate and reacted to obtain the polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating.

15. The preparation method according to claim 14, characterized in that: The NDJ-4 rotational viscosity of the mixture is 0.5-5.5 Pa.S, and the solid content of the mixture is above 55wt%; And / or, the ambient temperature when the mixture is applied to the substrate surface for reaction is -10-50°C; And / or, the reaction time when the mixture is applied to the surface of the substrate is 15 minutes to 24 hours.

16. A method for constructing a polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating on a substrate surface, characterized in that: include: Applying a tie layer composition at least once on the surface of the substrate to form a tie layer; The first component and the second component of the fouling resistance-release coating composition described in any one of claims 1 to 10 are uniformly mixed and applied to the surface of the tie layer for reaction to obtain a polyurethane epoxy modified silicone hydrogel fouling resistance-release coating.

17. The method according to claim 16, characterized in that: The tie layer composition includes a tie paint composition and / or a silicone-based primer composition; And / or, the mixture formed by the first component and the second component is coated on the surface of the tie layer 1-3 times by coating; wherein the dry film thickness of a single coat is above 100 μm.

18. Use of the fouling resistance-release coating composition according to any one of claims 1 to 10 or the polyurethane epoxy-modified silicone hydrogel fouling resistance-release coating according to any one of claims 12 to 13 in the field of antifouling engineering in marine environments.

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