Coating composition, its preparation method, and coating film

Abstract

To provide an asparagus polyurea resin system capable of forming a coating film having good antifouling effect, wearing resistance, impact resistance, corrosion resistance, good substrate wettability, high adhesion and other advantages.SOLUTION: An asparagus polyurea resin system includes a polymer with a structure represented by the formula below, where, X is derived from a polyaspartate resin, Y is derived from an isocyanate curing agent, and R is a group with antibacterial and antifouling function.SELECTED DRAWING: Figure 11

Description

[Technical Field]

[0001] (Related Applications) This application claims priority from Chinese Patent Application No. 202111083499.3, filed on September 15, 2021, and entitled "Asparagus polyurea resin system and coating composition with marine antifouling function."

[0002] (Technical field) The present application relates to coatings belonging to the technical field of functional polymer resins and functional coatings, in particular to an asparagus polyurea binder system and coating composition having marine antifouling function. [Background technology]

[0003] Marine biological pollution causes serious problems such as increased fuel consumption for ships, blockage of water pipes in nuclear power plants, and accelerated corrosion of metal surfaces. Marine antifouling materials, which act as the first line of defense against corrosion by marine organisms, are an important guarantee for the smooth development and operation of marine activities by humankind.

[0004] Humans have long struggled with marine organism fouling, and in the 1960s, tributyltin (TBT) coatings, which offered broad-spectrum antifouling capabilities, were developed. However, TBT was highly toxic to non-target organisms and was completely banned in 2008. Current antifouling coatings are typically tin-free, self-polishing coatings that use copper or zinc instead of organotins. However, copper-containing coatings are specific to only certain fouling species, and this drawback requires the addition of antifouling enhancers such as Irgarol 1051, copper pyrithione, and isothiazolinone. However, these technologies still release antifouling agents, which can pollute the marine environment or roughen the coating surface, forming a saponified layer, resulting in disadvantages in terms of durability and energy efficiency.

[0005] In recent years, harmless, non-polluting antifouling coatings have been attracting attention. Antifouling materials with low surface energy have a hydrophobic structure and can form an ultrahydrophobic layer on their surfaces. This prevents marine organisms from adhering to the material surface, or adhering poorly to it. They are then shed by the action of the ship's water currents, achieving antifouling effects. However, whether silicone resin or organic fluororesin, the coating surface has poor scratch resistance and is relatively expensive, making them unsuitable for large-scale applications. Furthermore, the diversity of marine organisms makes it difficult for organic fluororesin coatings to achieve a broad antifouling effect. In particular, the larger the surface contact angle (higher hydrophobicity), the more severe the adhesion of diatoms, bacteria C. marina, Ulva spores, and Pseudomonas aeruginosa.

[0006] Polyurea coatings have excellent mechanical properties, as well as excellent abrasion resistance, impact resistance, corrosion resistance, media resistance, and thermal stability, and are widely used in other fields such as rust prevention, waterproofing, wear resistance, vibration control, protection, and earthquake resistance. Compared with traditional environmental protection coating technologies, modified polyurea coatings are a new type of marine antifouling coating with great application potential.

[0007] In recent years, third-generation polyureas—polyaspartate polyureas—formed primarily by the mixed reaction of modified isocyanate prepolymers and polyaspartate resins—have been gaining attention. Polyaspartate resins are a type of secondary amine compound with a unique steric hindrance effect. Compared with conventional aliphatic amine resins, they have significantly lower activity and significantly improved substrate wetting and adhesion. However, significant challenges remain to be overcome in order to develop a polyaspartate resin antifouling system based on mature, commercially available asparagus polyureas, from the molecular design level, and to impart superior properties, such as antibacterial properties, low surface energy, and high mechanical strength, for better marine protection. Summary of the Invention [Problem to be solved by the invention]

[0008] The main objective of the present application is to provide an asparagus polyurea resin system with marine antifouling function, coating composition and its application to overcome the shortcomings of the prior art. [Means for solving the problem]

[0009] In order to achieve the above object of the invention, the present application provides the following technical solutions:

[0010] The present embodiment provides an asparagus polyurea resin system with marine antifouling functionality, which includes a polymer having the structure shown in the following formula:

[0011] [ka]

[0012] Here, X is derived from polyaspartate resin, Y is derived from isocyanate curing agent, and R is a group with antibacterial and antifouling functions.

[0013] The present embodiment provides an asparagus polyurea resin system with marine antifouling properties formed by reacting primarily polyaspartate resin, organic antifouling agent, polyether, polyisocyanate and organosilicon resin.

[0014] The present invention also provides a coating composition containing polyaspartate resin, organic antifouling agent, polyether, polyisocyanate, and organosilicon resin as ingredients.

[0015] The present examples further provide a method for preparing a coating composition, the method comprising: A step of blending raw materials according to the raw material composition of any one of the coating compositions of the present application; mixing the polyisocyanate and the organosilicon resin, reacting them at a certain temperature under a protective atmosphere, and then uniformly mixing the remaining raw materials to form a coating composition.

[0016] The examples of the present application further provide a coating composition prepared by any one of the above methods of the present application.

[0017] The examples of the present application further provide coatings formed from the above-described coating compositions of the present application. [Effects of the Invention]

[0018] Compared with the prior art, the technical solutions of the embodiments of the present application have at least the following advantages:

[0019] (1) The provided asparagus polyurea resin system with marine antifouling function has the advantages of low surface energy and excellent antibacterial properties, and has excellent antifouling and anticorrosion performance. It is not only environmentally friendly, but also has excellent mechanical properties such as abrasion resistance and impact resistance, making it suitable for a wide range of applications.

[0020] (2) The provided paint is solvent-free, i.e., 100% solids, safe and environmentally friendly, odorless, fast-curing, and can be coated on any curved, inclined, or vertical surface without sagging.

[0021] (3) The coating film formed from the paint is dense, seamless, and highly flexible, and has excellent antifouling properties, impact resistance, abrasion resistance, corrosion resistance, and chemical resistance (acid, alkali, salt, etc.). At the same time, it has excellent seawater resistance, good impact absorption, excellent heat resistance, wettability to substrates, and high adhesion, and can quickly adhere to substrates such as steel and concrete. It can be applied on a large scale to ships, offshore work platforms, submarine cables, water supply pipelines for nuclear power plants, etc., and is of great practical value. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is an infrared spectrum of the unmodified polyurea PUA coating film prepared in Comparative Example 1. [Figure 2] 1 is an infrared spectrum of the fluorosilicone modified polyurea PUA-FSi coating film prepared in Comparative Example 2. [Figure 3] 1 is an infrared spectrum of the organic antifouling agent-containing polyurea PUA-FSi-N coating film prepared in Example 1. [Figure 4] 1 is a photograph of the water contact angle of the unmodified polyurea PUA coating film prepared in Comparative Example 1. [Figure 5] 1 is a photograph of the water contact angle of the fluorosilicone-modified polyurea PUA-FSi coating film prepared in Comparative Example 2. [Figure 6] 1 is a photograph of the contact angle of the organic antifouling agent-containing polyurea PUA-FSi-N coating prepared in Example 1. [Figure 7] 1 is a photograph of the contact angle of an organosilicon antifouling coating film (PDMS) formed from a commercially available organosilicon antifouling paint. [Figure 8] FIG. 1 is a comparison diagram of the water contact angles of the PUA, PUA-FSi, and PUA-Fsi-N coatings prepared in Comparative Examples 1 and 2 and Example 1, and a PDMS coating. [Figure 9] FIG. 1 is a comparison diagram of the adhesion of the PUA, PUA-FSi, PUA-Fsi-N coatings prepared in Comparative Examples 1 and 2 and Example 1, and the PDMS coating to an epoxy primer. [Figure 10] 1 shows the stress-strain curves of the PUA, PUA-FSi, PUA-Fsi-N coatings and the PDMS coating prepared in Comparative Examples 1 and 2 and Example 1. [Figure 11] FIG. 1 is a comparison diagram of the Young's modulus of the PUA, PUA-FSi, and PUA-Fsi-N coatings prepared in Comparative Examples 1 and 2 and Example 1, and the PDMS coating. DETAILED DESCRIPTION OF THE INVENTION

[0023] In view of the above-mentioned many shortcomings of the prior art, the inventor of the present application has proposed the technical solution of the present application through long-term research and practice, which will be described in detail below.

[0024] An asparagus polyurea resin system with marine antifouling function provided by one embodiment of the present application has the following structure:

[0025] [ka]

[0026] Here, X is derived from polyaspartate resin, Y is derived from isocyanate curing agent, and R is a group with antibacterial and antifouling functions.

[0027] Another aspect of the present invention provides a method for preparing an asparagus polyurea resin system with marine antifouling properties, which comprises mixing a polyisocyanate and an organosilicon resin and carrying out a first reaction at 0-80°C under a protective atmosphere (e.g., a nitrogen atmosphere), followed by mixing with a polyaspartate resin, an organic antifouling agent, and a polyether and carrying out a second reaction at 0-50°C to obtain the target product. The reaction mechanism is as follows:

[0028] [ka] X: Fluorosilicone modified asparagus resin Y: Fluorosilicone modified isocyanate curing agent R: Group with antibacterial and antifouling properties

[0029] Furthermore, the mass ratio of polyisocyanate to organosilicon resin is 0-80:20-100, preferably 30-60:40-70.

[0030] Furthermore, the mass ratio of the polyaspartate resin, the organic antifouling agent, and the polyether is 0-80:0-50:0-50, preferably 30-60:10-30:10-30.

[0031] Furthermore, the mass ratio of the total mass of the polyaspartate resin, the organic antifouling agent and the polyether to the first reaction product is 1:0-10, preferably 1:0.5-2.

[0032] The amounts of polyaspartate resin, organic antifouling agent, polyether, and organic silicone resin added are all greater than zero.

[0033] Furthermore, the times for the first and second reactions are all greater than 0 hours but within 24 hours, preferably 3 to 12 hours.

[0034] Furthermore, the temperature of the first reaction is preferably 20 to 60°C.

[0035] Furthermore, the temperature of the second reaction is preferably 10 to 40°C.

[0036] The asparagus polyurea resin system of the present invention is preferably formed by reacting a fluorosilicone-modified polyaspartate resin, an organic antifouling agent, polyether, polyisocyanate, and an organic silicone resin, etc., and combines the advantages of the asparagus polyurea resin system, organic silicone polymer, quaternary ammonium salt, and polyether. It not only achieves synergistic antifouling properties due to its low surface energy and good antibacterial properties, but also has excellent corrosion resistance, abrasion resistance, and impact resistance, and has high adhesion, allowing it to quickly bond to substrates such as steel and concrete.

[0037] Another aspect of the present application provides an antifouling structure comprising an asparagus polyurea resin system having the marine antifouling function.

[0038] Furthermore, the antifouling structure can be a single layer coating or a multi-layer coating, one coating being based on the asparagus polyurea resin system having the marine antifouling function.

[0039] By forming the antifouling structure on the surface of a substrate, it is possible to achieve good protection of the substrate, and particularly to achieve good antifouling effect, The substrate may be made of various materials such as, but not limited to, metal, concrete, wood, polymer, or composite materials thereof.

[0040] Another aspect of the present application provides a coating composition comprising any one of the above asparagus polyurea resin systems.

[0041] In some embodiments, the asparagus polyurea resin system comprises 0.5% to 99% by weight of the coating composition dry film.

[0042] Alternatively, in some embodiments, the combined mass of the asparagus polyurea resin system and one or more antifouling agents comprises 0.5% to 99% of the weight of the coating composition dry film, wherein the antifouling agents include organic antifouling agents, inorganic antifouling agents, or combinations thereof, such as metal-dithiocarbamates, copper acrylates, metal antimicrobials, metal salts, heterocyclic nitrides, urea derivatives, amides or imides of carboxylic acids, sulfonic and sulfinic acids, salts or esters of carboxylic acids, substituted benzenes, guanidine derivatives, butenolide derivatives, imidazole-containing compounds, and the like.

[0043] In some embodiments, the coating composition is a solventless system.

[0044] Another aspect of the present application further provides a coating composition made from polyaspartate resin, organic antifouling agent, polyether, polyisocyanate, organosilicon resin, etc., and may further contain optional added or non-added ingredients such as fillers and auxiliaries.

[0045] In some embodiments, the coating composition is a solventless system.

[0046] In some embodiments, the raw materials of the coating composition include 0 to 80 parts by weight of polyaspartate resin, 0 to 50 parts by weight of organic antifouling agent, 0 to 50 parts by weight of polyether, 0 to 80 parts by weight of organosilicon resin, and 20 to 100 parts by weight of polyisocyanate, and the added amounts of the polyaspartate resin, organic antifouling agent, polyether, and organosilicon resin are all greater than 0.

[0047] In some embodiments, the coating composition comprises a first component and a second component; The first component further comprises a polyaspartate resin, an organic antifouling agent, a polyether, and additional or non-additive components (e.g., fillers, auxiliary agents, etc.); The second component is made from polyisocyanate and organosilicon resin.

[0048] In some embodiments, the first component comprises 0 to 80 parts by weight of a polyaspartate resin, 0 to 50 parts by weight of an organic antifouling agent, and 0 to 50 parts by weight of a polyether.

[0049] In some embodiments, the second component ingredients include 0 to 80 parts by weight of an organosilicon resin and 20 to 100 parts by weight of a polyisocyanate.

[0050] In some embodiments, the mass ratio of the first component to the second component is 1:0-10, and the amount of the second component added is greater than zero.

[0051] Here, the amounts of the polyaspartate resin, the organic antifouling agent, the polyether, and the organic silicone resin added are all greater than zero.

[0052] Preferably, the first component contains 30 to 60 parts by weight of polyaspartate resin, 10 to 30 parts by weight of organic antifouling agent, and 10 to 30 parts by weight of polyether.

[0053] Preferably, the second component contains 30 to 60 parts by weight of polyisocyanate and 40 to 70 parts by weight of organosilicon resin.

[0054] Preferably, the mass ratio of the first component to the second component is 1:0.5-2.

[0055] In some embodiments, the polyaspartate resin has the following structure:

[0056] [ka]

[0057] Here, R1 is an aliphatic hydrocarbon group having more than 0 and 100 or less carbon atoms, and R2 is a fluorine-containing hydrocarbon group or a silicon-containing hydrocarbon group having more than 0 and 100 or less carbon atoms.

[0058] Furthermore, the polyaspartate resin may include, but is not limited to, one or more of the following: polyaspartate resin, fluorine-containing polyaspartate resin, silicon-containing polyaspartate resin, and fluorine-containing silicon-modified polyaspartate resin. One of the modified polyaspartate resins is produced by the following reaction:

[0059] [ka]

[0060] Further, the organic antifouling agent may include, but is not limited to, any one or more combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine derivatives, butyl lactone, butyl lactone derivatives, alkyldimethylbenzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, di(hydroxyethyl)methyldodecylammonite, and di(2-hydroxyethyl)methyltetradecyl chloride quaternary ammonium salts.

[0061] Furthermore, the polyether may include, but is not limited to, any one or more combinations of polyethylene glycol, polyethylene glycol monomethyl ether, poly(ethylene glycol) methyl ether amine, polypropylene glycol, polypropylene glycol monomethyl ether, and polyether amine.

[0062] In some embodiments, the first component comprises one or more of the following: fillers, adjuvants, and a combination thereof.

[0063] Furthermore, the first component contains 0 to 50 parts by weight of a filler and 0 to 20 parts by weight of an auxiliary agent.

[0064] Additionally, the filler may include, but is not limited to, any one or more combinations of pyrite, barium sulfate, titanium dioxide, silica powder, talc, and calcium carbonate.

[0065] Additionally, the auxiliary agents include, but are not limited to, any one or more combinations of leveling agents, defoamers, dispersants, thickeners, coupling agents, and activating powders.

[0066] In some embodiments, the organosilicon resin includes, but is not limited to, any one or more combinations of the following compounds:

[0067] [ka] Here, n is 10 to 1000.

[0068] In some embodiments, the polyisocyanate includes, but is not limited to, any one or more combinations of hexamethylene diisocyanate trimer, fluorosilicone modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorosilicone modified L-lysine triisocyanate, triphenylmethane triisocyanate, and fluorosilicone modified triphenylmethane triisocyanate.

[0069] Another aspect of the present application further provides a method for preparing a coating composition, the method comprising: A step of blending raw materials according to the raw material composition of the coating composition; and mixing the polyisocyanate and the organosilicon resin, reacting them at 0 to 80°C for 0 to 24 hours in a protective atmosphere (e.g., a nitrogen atmosphere), and then uniformly mixing the mixture with the remaining raw materials at a temperature of 0 to 50°C to form a coating composition.

[0070] In some embodiments, the coating composition employs a two-component design, i.e., comprises the first and second components described above. Correspondingly, the preparation method thereof comprises: A step of blending raw materials according to the raw material composition of the coating composition; uniformly mixing all materials for forming the first component to form the first component; mixing the polyisocyanate and the organosilicon resin and reacting them under a protective atmosphere (e.g., a nitrogen atmosphere) at 0-80°C for 0-24 hours to form a second component; and combining and uniformly mixing the first and second components at a temperature of 0 to 50°C to form a coating composition.

[0071] The coating composition is solvent-free, i.e., 100% solids, safe and environmentally friendly, odorless, fast curing, and can be coated on any curved, inclined, or vertical surface without sagging.

[0072] Another aspect of the present application further provides a coating film formed from the coating composition, which is dense, seamless, and highly flexible, and has excellent antifouling properties, impact resistance, abrasion resistance, corrosion resistance, and chemical resistance (acid, alkali, salt, etc.), as well as excellent seawater resistance, good impact absorption, excellent heat stability, wettability to substrates, high adhesion, and can quickly adhere to substrates such as steel and concrete.

[0073] Another aspect of the present application provides a method for preparing a coating film, the method comprising the step of applying the coating composition to a substrate surface and drying to form a coating film. The coating can be applied to the substrate surface by a method such as blade coating, spin coating, spraying, or printing. The substrate can be metal, concrete, wood, polymer, or a composite material thereof.

[0074] The coating film of the present application has advantages such as good antifouling effect, abrasion resistance, impact resistance, corrosion resistance, good wettability to substrates, and high adhesion, and can be used on large ships, offshore work platforms, nuclear power plants, etc., and can provide excellent long-term antifouling, antirust, abrasion resistance, corrosion resistance, impact resistance, shock absorption, and temperature change resistance.

[0075] The present invention will be further described with reference to examples to clarify the objectives, technical solutions, and advantages of the present application, but the examples are not intended to limit the scope of protection of the present invention. Furthermore, unless otherwise specified, the various raw materials used in the following examples can be purchased from the market or prepared by yourself according to reference books in the relevant field, and the various manufacturing and testing equipment used are known equipment available in the relevant field.

[0076] Some of the raw materials used in the following examples and comparative examples can be obtained as follows.

[0077] Dispersant GA264, Zhongshan Worth Chemical Co., Ltd.

[0078] Pigment 4920 Pyrite, LANXESS Chemical (China) Co., Ltd.

[0079] Filler 1250 mesh barium sulfate, Shanghai Kaiyin Chemical Co., Ltd.

[0080] Anti-sagging agent H15, Wacker Chemie(China) Co., Ltd.

[0081] Moisture-proofing agent A3 powder, Zhengzhou Fulong New Material Technology Co., Ltd.

[0082] Antifoam agent BYK085, Wacker Chemie(China) Co., Ltd.

[0083] Leveling agent TEGO450, Shanghai Kaiyin Chemical Co., Ltd.

[0084] Silane coupling agent KH560, Shandong Qufu Chengguang Chemical Co., Ltd.

[0085] Rheological aid BYK410, Wacker Chemie(China) Co., Ltd.

[0086] Light stabilizers 1130 and 292, BASF (China) Co., Ltd.

[0087] Dehydrating agent BF-5, Shanghai Deyu Trading Co., Ltd.

[0088] Tackifier GB950-90, Shenzhen Feiyang Junken New Materials Co., Ltd.

[0089] Of course, the various ingredients listed above can be substituted with other ingredients described herein.

[0090] The measurement methods used in the following examples are as follows.

[0091] (1) Using a Nicolet Instrument Co. USA Fourier transform microscope infrared spectrophotometer (Nicolet iN10), infrared measurements of the raw materials and the degree of cure of the coating film of the examples are carried out.

[0092] (2) The water contact angle of the coating film is measured using a video optical contact angle measuring instrument (OCA15EC) manufactured by Dataphysics, Germany.

[0093] (3) The mechanical properties of the coating film are measured using a material testing machine (Instron 3365) manufactured by Instron Corporation, USA.

[0094] (Comparative Example 1) The method for preparing the polyaspartate polyurea coating includes the following steps:

[0095] (1) Preparation of component A of the paint: At room temperature, 42 parts by weight of polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed uniformly and then high-speed dispersed for 30 minutes (high-speed dispersion refers to a dispersion speed of 1500 rpm or more, the same applies below), then polished to 30 μm or less, and 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B, and 6 parts by weight of the solvent butyl acetate were added and high-speed dispersed for 10 minutes.

[0096] (2) Prepared paint component B: At room temperature, 9.5 parts by weight of solvent butyl acetate, 0.5 parts by weight of dehydrating agent, 76.5 parts by weight of hexamethylene diisocyanate trimer (Wanhua Chemical Group Co., Ltd.), and 13.5 parts by weight of tackifier were mixed and dispersed at high speed for 5 minutes.

[0097] (3) At room temperature, the above components A and B are uniformly mixed in a weight ratio of 1:0.37 to form a coating material.

[0098] (Comparative Example 2) The method for preparing the fluorosilicone modified polyaspartate polyurea coating includes the following steps:

[0099] (1) Preparation of component A of the paint: At room temperature, 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed uniformly, and then high-speed dispersed for 30 minutes at a dispersion speed of 1500 r / min and polished to 30 μm or less. Then, 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B, and 6 parts by weight of butyl acetate were added, and high-speed dispersed for 10 minutes.

[0100] (2) Component B of the prepared paint: At room temperature, 9.5 parts by weight of butyl acetate, 0.5 parts by weight of dehydrating agent, 76.5 parts by weight of hexamethylene diisocyanate trimer (Wanhua Chemical Group Co., Ltd.), and 13.5 parts by weight of tackifier are mixed and dispersed at high speed for 5 minutes.

[0101] (3) At room temperature, the above components A and B are uniformly mixed in a weight ratio of 1:0.29 to form a paint.

[0102] (Comparative Example 3) A method for preparing a fluorosilicone modified polyaspartate polyurea coating, comprising the steps of:

[0103] (1) Preparation of component A of the paint: At room temperature, 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed uniformly and then high-speed dispersed for 30 minutes at a dispersion speed of 1500 r / min and polished to below 30 μm. Then, 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B, and 6 parts by weight of butyl acetate were added and high-speed dispersed for 10 minutes.

[0104] (2) Prepared paint component B: At room temperature, 9.5 parts by weight of butyl acetate, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of hexamethylene diisocyanate trimer (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier were mixed and dispersed at high speed for 5 minutes.

[0105] (3) At room temperature, the above components A and B are mixed uniformly in a weight ratio of 1:0.5 to form a paint.

[0106] Comparative Example 4 The process for preparing the fluorosilicone modified organic antifouling agent-containing polyaspartate polyurea coating includes the following steps:

[0107] (1) Preparation of component A of the paint: At room temperature, 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 10 parts by weight of di(hydroxyethyl)methyldodecyl ammonite, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min, and polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B, and 6 parts by weight of butyl acetate were added and dispersed at high speed for 10 minutes.

[0108] (2) Prepared paint component B: At room temperature, 9.5 parts by weight of butyl acetate, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier were mixed and dispersed at high speed for 5 minutes.

[0109] (3) At room temperature, the above components A and B are uniformly mixed in a weight ratio of 1:1.2 to form a coating material.

[0110] (4) Under room temperature conditions, the paint was scraped off from a tin substrate with a film thickness of 200 μm, and its performance was measured. The results were an activation time of 14 minutes, a surface drying time at 25°C of 14 minutes, an actual drying time at 25°C of 30 minutes, and a hardness of H.

[0111] (Comparative Example 5) The preparation process for the fluorosilicone modified organic antifouling agent-containing polyaspartate polyurea coating includes the following steps:

[0112] (1) Preparation of component A of the paint: At room temperature, 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 20 parts by weight of pigment, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min, and polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B, and 6 parts by weight of butyl acetate were added and dispersed at high speed for 10 minutes.

[0113] (2) Prepared paint component B: At room temperature, 9.5 parts by weight of butyl acetate, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier were mixed and dispersed at high speed for 5 minutes.

[0114] (3) At room temperature, the above components A and B are uniformly mixed in a weight ratio of 1:1.2 to form a coating material.

[0115] (Comparative Example 6) The preparation process for the fluorosilicone modified organic antifouling agent-containing polyaspartate polyurea coating includes the following steps:

[0116] (1) Preparation of component A of the paint: At room temperature, 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 10 parts by weight of di(hydroxyethyl)methyl dodecyl ammonite, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min, and polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B, and 6 parts by weight of butyl acetate were added and dispersed at high speed for 10 minutes.

[0117] (2) Prepared paint component B: At room temperature, 9.5 parts by weight of butyl acetate, 0.5 parts by weight of dehydrating agent, 76.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.), and 13.5 parts by weight of tackifier were mixed and dispersed at high speed for 5 minutes.

[0118] (3) At room temperature, the above components A and B are uniformly mixed in a weight ratio of 1:1.1 to form a coating material.

[0119] Example 1 The process for preparing the asparagus polyurea resin system coating containing fluorosilicone modified organic antifouling agent includes the following steps:

[0120] (1) Preparation of component A of the paint: At room temperature, 48 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 5 parts by weight of di(hydroxyethyl)methyl dodecyl ammonite, 5 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min and polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0121] (2) Prepared paint component B: At room temperature, 0.5 parts by weight of a dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of a tackifier were mixed and dispersed at high speed for 5 minutes.

[0122] (3) At room temperature, the above components A and B are uniformly mixed in a weight ratio of 1:1 to form a coating material.

[0123] Example 2 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0124] Preparation of component A of the paint: At room temperature, 48 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 10 parts by weight of di(hydroxyethyl)methyl dodecyl ammonite, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min. The mixture was polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B8 were added and dispersed at high speed for 10 minutes.

[0125] Prepared paint component B: Mix 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier at 60°C and disperse at high speed for 5 minutes.

[0126] The above components A and B are mixed uniformly at a weight ratio of 1:1.5 at room temperature to form a coating material.

[0127] Example 3 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0128] Preparation of component A of the paint: At room temperature, 48 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 20 parts by weight of di(hydroxyethyl)methyl dodecyl ammonite, 20 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min. The mixture was polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0129] Prepared paint component B: Mix 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier at 60°C and disperse at high speed for 5 minutes.

[0130] The above components A and B are mixed uniformly at a weight ratio of 1:2 at room temperature to form a coating material.

[0131] Example 4 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0132] Preparation of paint component A: At room temperature, 48 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 30 parts by weight of di(hydroxyethyl)methyl dodecyl ammonite, 30 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min. The mixture was polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0133] Preparation of paint component B: At 65°C, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier were mixed and dispersed at high speed for 5 minutes.

[0134] The above components A and B are mixed uniformly at a weight ratio of 1:3 under room temperature conditions to form a coating material.

[0135] Example 5 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0136] Preparation of paint component A: At room temperature, 48 parts by weight of polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 10 parts by weight of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (Econea), 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min. The mixture was polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0137] Prepared paint component B: Mix 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier at 60°C and disperse at high speed for 5 minutes.

[0138] The above components A and B are mixed uniformly at a weight ratio of 1:1.5 at room temperature to form a coating material.

[0139] Example 6 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0140] Preparation of component A of the paint: At a temperature of about 40°C, 48 parts by weight of silicon-containing polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 10 parts by weight of N-(2,4,6-trichlorophenyl)maleimide (TCM), 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min, and polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0141] Prepared paint component B: Mix 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier at 80°C and disperse at high speed for 5 minutes.

[0142] At a temperature of about 40°C, the above components A and B are mixed uniformly in a weight ratio of 1:1.5 to form a paint.

[0143] Example 7 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0144] Preparation of paint component A: At room temperature, 48 parts by weight of fluorine-containing polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 20 parts by weight of pigment, 0.1 parts by weight of medetomidine, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min. The mixture was polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0145] Prepared paint component B: Mix 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier at 60°C and disperse at high speed for 5 minutes.

[0146] At a temperature of about 50°C, the above components A and B are mixed uniformly in a weight ratio of 1:1.2 to form a paint.

[0147] Example 8 The preparation process of the organic antifouling agent-containing asparagus polyurea resin system coating provided in this example is basically the same as that in Example 1, except for the following points:

[0148] Preparation of paint component A: At room temperature, 48 parts by weight of polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 20 parts by weight of pigment, 10 parts by weight of copper pyrithione, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of moisture-proofing agent, 0.2 parts by weight of antifoaming agent A, and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes at a dispersion speed of 1500 r / min. The mixture was polished to 30 μm or less. 0.1 parts by weight of leveling agent A, 0.1 parts by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were added and dispersed at high speed for 10 minutes.

[0149] Prepared paint component B: Mix 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wacker Chemical Group Co., Ltd.), 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.), and 13.5 parts by weight of tackifier at 60°C and disperse at high speed for 5 minutes.

[0150] The above components A and B are mixed uniformly at a weight ratio of 1:1.5 at room temperature to form a coating material.

[0151] The coatings of Comparative Example 1, Comparative Example 2, and Example 1 consisted of unmodified polyurea PUA, fluorosilicone-modified polyurea PUA-FSi, and organic antifouling agent-containing polyurea PUA-FSi-N, respectively. Their infrared spectra are shown in Figures 1, 2, and 3, respectively. In Figure 1, PUA(A) is the unmodified asparagus polyurea resin, and PUA(B) is the unmodified asparagus polyurea resin curing agent. PUA was formed by mixing PUA(A) and PUA(B) and curing. In Figure 2, PUA-FSi(A) is the fluorosilicone-modified asparagus polyurea resin, and PUA(B) is the fluorosilicone-modified asparagus polyurea resin curing agent. PUA was formed by mixing PUA-FSi(A) and PUA(B) and fully curing them. PUA-FSi-N(A) in Figure 3 is a fluorosilicone-modified asparagus polyurea resin, and PUA-FSi-N(B) is a fluorosilicone-modified asparagus polyurea resin curing agent. PUA-FSi-N is formed by mixing PUA-FSi-N(A), an organic quaternary ammonium salt, and PUA-FSi-N(B) and curing the mixture. As can be seen from Figures 1 to 3, each of the resulting coating films exhibited a υ- NCO =2267cm -1 The characteristic peak completely disappeared, and the urea bond υ- NH =1658cm -1 A characteristic peak was produced, proving that the coating was fully cured.

[0152] Figures 4, 5, and 6 show photographs of the water contact angles of the coatings of Comparative Example 1, Comparative Example 2, and Example 1, respectively. As a control, an antifouling coating film was formed from a commercially available organosilicon antifouling paint under the conditions of Example 1, and a photograph of the water contact angle is shown in Figure 7. As a result, the water contact angle of the fluorosilicone-modified polyurea PUA-FSi increased from 90.5 degrees for the unmodified polyurea PUA to 108.8 degrees, which is relatively close to the contact angle of 112.9 degrees for an organosilicon antifouling coating (PDMS coating) formed from a commercially available organosilicon antifouling paint. This indicates that the fluorosilicone-modified polyurea PUA-FSi is a coating with excellent performance and low surface energy. The water contact angle of the organic antifouling agent-containing polyurea PUA-FSi-N, to which antifouling groups have been grafted, decreased from 108.8 degrees to 61.7 degrees. This indicates that a hydrophilic hydrogel is formed on the surface of the coating based on the fluorosilicone-modified polyurea PUA-FSi, and the organic antifouling agent is enriched on the surface of the coating.

[0153] Furthermore, the water contact angle measurement results of the above-mentioned unmodified polyurea PUA, fluorosilicone-modified polyurea PUA-FSi, organic antifouling agent-containing polyurea PUA-FSi-N coating film, and organosilicon antifouling coating film (PDMS) formed from a commercially available organosilicon antifouling paint are also shown in Figure 8.

[0154] Figure 9 shows a comparison of the adhesive properties of the above-mentioned unmodified polyurea PUA, fluorosilicone-modified polyurea PUA-FSi, organic antifouling agent-containing polyurea PUA-FSi-N coating, and PDMS coating with epoxy primer. The organic antifouling agent-containing polyurea PUA-FSi-N coating and epoxy primer have 50 times better adhesiveness than the organic silicon antifouling coating without a link coating, which can reduce the number of processes and further reduce construction costs in actual construction.

[0155] Figures 10 and 11 compare the mechanical properties, such as stress-strain and Young's modulus, of the unmodified polyurea PUA, the fluorosilicone-modified polyurea PUA-FSi, the organic antifouling agent-containing polyurea PUA-FSi-N coating, and the PDMS coating, respectively. As can be seen from the figures, the organic antifouling agent-containing polyurea PUA-FSi-N coating has superior mechanical properties, with a Young's modulus 1,400 times that of the PDMS coating, significantly improving the coating's scratch resistance.

[0156] The properties of the paints obtained in Comparative Examples 1 to 5 and Examples 1 to 8 and the coating films formed therefrom are shown in Tables 1 and 2, respectively.

[0157] (Paint properties) [Table 1]

[0158] (Coating film characteristics) [Table 2]

[0159] The coating and film properties in the examples and comparative examples were measured using national standards GB / T 6822-2014 and HG / T 3831-2006. The chemical resistance test items in Table 2 include salt resistance for 240 hours (3% NaCl solution), alkali resistance for 240 hours (5% NaOH solution), acid resistance for 240 hours (5% H2SO4 solution), and water resistance for 30 days (25°C).

[0160] Example 9 The synthesis method for an asparagus polyurea resin system with marine antifouling properties involves the following steps: At room temperature, 66.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.) and 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.) are mixed and high-speed dispersed for 5 minutes. Then, 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 5 parts by weight of di(hydroxyethyl)methyl dodecyl ammonite, and 5 parts by weight of polyethylene glycol monomethyl ether are added and high-speed dispersed for 10 minutes to obtain the target product. The infrared spectrum of this target product is similar to that of PUA-FSi-N in Example 1.

[0161] Example 10 The synthesis of an asparagus polyurea resin system with marine antifouling properties involves the following steps: 66.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.) and 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.) are mixed and high-speed dispersed at 60°C for 5 minutes, and the resulting reaction product is then mixed at room temperature with 42 parts by weight of fluorosilicone-modified polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 10 parts by weight of di(hydroxyethyl)methyldodecyl ammonite, and 10 parts by weight of polyethylene glycol monomethyl ether, and the resulting product is then high-speed dispersed for 30 minutes.

[0162] Example 11 The synthesis of an asparagus polyurea resin system with marine antifouling properties involves the following steps: 66.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.) and 10 parts by weight of amino-terminated dimethicone (Wacker Chemie (China) Co., Ltd.) are mixed and high-speed dispersed at 80°C for 5 minutes, and the resulting reaction product is then mixed at room temperature with 42 parts by weight of polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 10 parts by weight of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (Econea), and 10 parts by weight of polyethylene glycol monomethyl ether, and the resulting product is obtained by continuously high-speed dispersing for 30 minutes.

[0163] The properties of the target products of Examples 9 to 11 were measured according to the methods of Examples 1 to 8, and it was found that the products had excellent properties such as breaking elongation, water contact angle, surface energy, abrasion resistance, and antifouling properties.

[0164] The above is only a preferred embodiment of the present application, and is not intended to limit the present application. Those skilled in the art may make various improvements and modifications without departing from the technical principles of the present application, and all such improvements and modifications shall fall within the scope of protection of the present application.

[0165] (Addendum) (Appendix 1) The polymer comprises a polymer having a structure represented by the formula: [ka] An asparagus polyurea resin system with marine antifouling function, characterized in that X is derived from polyaspartate resin, Y is derived from an isocyanate curing agent, and R is a group having antibacterial and antifouling functions.

[0166] (Appendix 2) An asparagus polyurea resin system having marine antifouling properties, characterized in that it is formed by reacting polyaspartate resin, an organic antifouling agent, polyether, polyisocyanate, and an organic silicone resin as main components.

[0167] (Appendix 3) The polyaspartate resin includes one or more combinations of polyaspartate resin, fluorine-containing polyaspartate resin, silicon-containing polyaspartate resin, and fluorine-containing silicon-modified polyaspartate resin; and / or the organic antifouling agent comprises any one or more combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine derivatives, butyl lactone, butyl lactone derivatives, alkyldimethylbenzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, di(hydroxyethyl)methyldodecylammonite, and di(2-hydroxyethyl)methyltetradecyl chloride quaternary ammonium salts; and / or the polyether comprises any one or more combinations of polyethylene glycol, polyethylene glycol monomethyl ether, poly(ethylene glycol) methyl ether amine, polypropylene glycol, polypropylene glycol monomethyl ether, and polyether amine; and / or the organosilicon resin comprises any one or more combinations of the following compounds: [ka] where n is 10 to 1000, and / or the polyisocyanate comprises one or more combinations of hexamethylene diisocyanate trimer, fluorosilicone-modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorosilicone-modified L-lysine triisocyanate, triphenylmethane triisocyanate, and fluorosilicone-modified triphenylmethane triisocyanate.

[0168] (Appendix 4) A coating composition comprising the asparagus polyurea resin system according to any one of claims 1 to 3.

[0169] (Appendix 5) 5. The coating composition of claim 4, wherein the asparagus polyurea resin system comprises 0.5% to 99% of the dry film weight of the coating composition, or wherein the combined mass of the asparagus polyurea resin system and one or more antifouling agents comprises 0.5% to 99% of the dry film weight of the coating composition, and / or the coating composition is a solventless system.

[0170] (Appendix 6) A coating composition, characterized in that the raw materials of the coating composition comprise 0 to 80 parts by weight of a polyaspartate resin, 0 to 50 parts by weight of an organic antifouling agent, 0 to 50 parts by weight of a polyether, 0 to 80 parts by weight of an organic silicone resin, and 20 to 100 parts by weight of a polyisocyanate, wherein the added amounts of the polyaspartate resin, the organic antifouling agent, the polyether, and the organic silicone resin are all greater than 0.

[0171] (Appendix 7) The polyaspartate resin has the following structure: [ka] wherein R1 is selected from aliphatic hydrocarbon groups, preferably C1-C100 aliphatic hydrocarbon groups, and R2 is selected from fluorine- or silicon-containing hydrocarbon groups, preferably C1-C100 fluorine- or silicon-containing hydrocarbon groups.

[0172] (Appendix 8) The polyaspartate resin includes any one or more combinations of polyaspartate resin, fluorine-containing polyaspartate resin, silicon-containing polyaspartate resin, and fluorine-containing silicon-modified polyaspartate resin; and / or the organic antifouling agent comprises any one or more combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine derivatives, butyl lactone, butyl lactone derivatives, alkyldimethylbenzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, di(hydroxyethyl)methyldodecylammonite, and di(2-hydroxyethyl)methyltetradecyl chloride quaternary ammonium salts; and / or the polyether comprises any one or more combinations of polyethylene glycol, polyethylene glycol monomethyl ether, poly(ethylene glycol) methyl ether amine, polypropylene glycol, polypropylene glycol monomethyl ether, and polyether amine; and / or the organosilicon resin comprises any one or more combinations of the following compounds: [ka] where n is 10 to 1000, and / or the polyisocyanate comprises one or more combinations of hexamethylene diisocyanate trimer, fluorosilicone-modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorosilicone-modified L-lysine triisocyanate, triphenylmethane triisocyanate, and fluorosilicone-modified triphenylmethane triisocyanate.

[0173] (Appendix 9) The coating composition of claim 6, wherein the raw materials of the coating composition include one or more combinations of fillers and auxiliaries, and / or the coating composition is a solvent-free system.

[0174] (Appendix 10) The raw materials of the coating composition further include 0 to 50 parts by weight of a filler and 0 to 20 parts by weight of an auxiliary agent; and / or the filler comprises one or more combinations of pyrite, barium sulfate, titanium dioxide, silica powder, talc, and calcium carbonate; and / or the auxiliary agent comprises one or more combinations of a leveling agent, a defoaming agent, a dispersing agent, a thickening agent, a coupling agent, and an activating powder.

[0175] (Appendix 11) A step of blending raw materials according to the raw material composition of the coating composition described in any one of Supplementary Notes 6 to 10; and mixing a polyisocyanate and an organosilicon resin, reacting them at 0 to 80°C under a protective atmosphere, and then uniformly mixing the resulting mixture with the remaining raw materials to form a coating composition.

[0176] (Appendix 12) A coating film formed from the coating composition according to any one of appendices 4 to 10.

Claims

1. A coating composition, the raw materials of which include 48 to 80 parts by weight of a polyaspartate resin, 10 to 50 parts by weight of an organic antifouling agent, 10 to 50 parts by weight of a polyether, 10 to 80 parts by weight of an organosilicon resin, and 20 to 100 parts by weight of a polyisocyanate; The polyaspartate resin has the following structure: 【Chemical 1】 (In the formula, R １ is an aliphatic hydrocarbon group. the organic antifouling agent is any one or a combination of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine derivatives, butyl lactone, butyl lactone derivatives, alkyldimethylbenzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, di(hydroxyethyl)methyldodecylammonite, and di(2-hydroxyethyl)methyltetradecyl chloride quaternary ammonium salts; and the polyether comprises polyethylene glycol monomethyl ether; The organosilicon resin is composed of one or more combinations of the following compounds: 【Chemistry 2】 (In the formula, n is 10 to 1000.) and the polyisocyanate is selected from the group consisting of hexamethylene diisocyanate trimer, fluorosilicone-modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorosilicone-modified L-lysine triisocyanate, triphenylmethane triisocyanate, and fluorosilicone-modified triphenylmethane triisocyanate, and a combination of any one or more thereof. Paint composition.

2. A coating composition, the raw materials of which include 48 to 80 parts by weight of a polyaspartate resin, 10 to 50 parts by weight of an organic antifouling agent, 10 to 50 parts by weight of a polyether, 10 to 80 parts by weight of an organosilicon resin, and 20 to 100 parts by weight of a polyisocyanate; The polyaspartate resin has the following structure: 【Chemistry 3】 the organic antifouling agent is any one or a combination of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine derivatives, butyl lactone, butyl lactone derivatives, alkyldimethylbenzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, di(hydroxyethyl)methyldodecylammonite, and di(2-hydroxyethyl)methyltetradecyl chloride quaternary ammonium salts; and the polyether comprises polyethylene glycol monomethyl ether; The organosilicon resin is composed of one or more combinations of the following compounds: 【Chemistry 4】 (In the formula, n is 10 to 1000.) and the polyisocyanate is selected from the group consisting of hexamethylene diisocyanate trimer, fluorosilicone-modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorosilicone-modified L-lysine triisocyanate, triphenylmethane triisocyanate, and fluorosilicone-modified triphenylmethane triisocyanate, and a combination of any one or more thereof. Paint composition.

3. A paint composition as described in claim 1 or claim 2, comprising a composition obtained by combining and uniformly mixing a first component comprising a mixture of the polyaspartate resin, the organic antifouling agent, and the polyether with a second component comprising a mixture of the organic silicone resin and the polyisocyanate.

4. 3. The coating composition of claim 1 or claim 2, wherein the raw materials of the coating composition include one or more combinations of fillers, auxiliaries, and / or the coating composition is a solvent-free system.

5. The filler comprises one or more combinations of pyrite, barium sulfate, titanium dioxide, silica powder, talc, and calcium hydroxide; And / or the auxiliary agent comprises any one or more combinations of a leveling agent, a defoaming agent, a dispersing agent, a thickener, a coupling agent, and an activating powder.

6. A step of blending raw materials according to the raw material composition of the coating composition according to any one of claims 1 to 5; and mixing the polyisocyanate and the organosilicon resin, reacting them at 0 to 80°C under a nitrogen atmosphere, and then uniformly mixing the resulting mixture with the remaining raw materials to form a coating composition.

7. A coating film formed from the coating composition according to any one of claims 1 to 5.

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