Coating composition, application thereof and ship

Abstract

The invention provides a coating composition and application thereof and a ship, the coating composition comprises a first coating, a second coating located on the surface of the first coating and a third coating located on the surface of the second coating, the first coating comprises an epoxy polymer, the second coating comprises aromatic polyurea, the third coating comprises aliphatic polyurethane, and the first coating and the second coating are bonded together. Wherein the side chain of the epoxy polymer comprises hydroxyl. The coating composition has excellent corrosion resistance, scratch resistance, wear resistance and yellow aging resistance.

Description

Technical Field

[0001] The present application relates to the field of ship technology, and in particular to a coating composition and its application, and a ship. Background Art

[0002] Ships are man-made vehicles that primarily operate in natural waters. Navigating in seawater, ships are extremely susceptible to corrosion from the seawater, which can lead to corrosion and cracking of the outer hull, affecting the ship's normal operation. Furthermore, conventional coatings on the outer hull of ships lack scratch and wear resistance. While docked at a pier, ships often scrape against the dock or the rubber fenders above it, causing wear and tear on the outer hull's paint. Seawater easily penetrates through the coating damage, and capillary action and the secretion of corrosive substances by microorganisms further accelerate the aging and peeling of the coating, leading to corrosion of the hull. Improving the corrosion resistance of the outer hull of ships has become a technical issue that urgently needs to be addressed. Summary of the Invention

[0003] This application is made in view of the above-mentioned problems, and its purpose is to provide a coating composition and its application, and a ship. The coating composition has excellent corrosion resistance, scratch resistance, wear resistance, and yellowing and deformation resistance, and can be long-term adhered to the outer hull of a ship, thereby increasing the service life of the ship.

[0004] The first aspect of the present application provides a coating composition, comprising a first coating, a second coating located on the surface of the first coating, and a third coating located on the surface of the second coating, wherein the first coating comprises an epoxy polymer, the second coating comprises an aromatic polyurea, and the third coating comprises an aliphatic polyurethane, wherein the side chains of the epoxy polymer comprise hydroxyl groups.

[0005] The first coating layer comprising epoxy polymer has good bonding strength with the outer hull of the ship, so that the coating composition can be permanently attached to the outer hull. At the same time, the side chain group hydroxyl group of the epoxy polymer can also react and combine with the isocyanate group of the aromatic polyurea in the second coating layer, so that the first coating layer and the second coating layer have excellent adhesion and can also improve the long-term adhesion of the second coating layer; the second coating layer comprising aromatic polyurea has excellent scratch and wear resistance, reducing the damage of the coating composition caused by scratches on the outer hull. At the same time, the high cross-linking density of the aromatic polyurea itself can effectively reduce the penetration and swelling of small molecules, reduce the corrosion effect of corrosive substances in seawater on the outer hull, and improve the anti-corrosion effect of the coating composition; the aliphatic polyurethane in the third coating layer mainly functions to improve the aging and yellowing resistance of the coating composition. At the same time, the hydroxyl group and isocyanate group in the aliphatic polyurethane can undergo cross-linking reaction with the isocyanate group and amine group in the polyurea to form good bonding strength, thereby improving the adhesion of the coating.

[0006] In summary, the coating composition of the present application includes three layers of coating, and the polymers in each coating are matched with each other to improve the long-term adhesion of the coating composition to the outer hull, improve the corrosion resistance, scratch resistance, wear resistance, yellowing resistance and aging resistance of the coating composition, and extend the service performance of the outer hull of the ship.

[0007] In any embodiment, the aromatic polyurea is formed by polymerizing a first component and a second component, wherein the first component comprises an aromatic primary amino-terminated polyether, a diamine compound, and a secondary amino-terminated polyether; and the second component comprises an aromatic isocyanate compound.

[0008] Aromatic polyureas are produced by the reaction of an aromatic isocyanate compound (a second component) with an amino compound (a first component). The amino compound (a first component) contains both primary-terminated and secondary-terminated amino polyethers, which can regulate the reaction rate between the amino group and the isocyanate, achieving a moderate reaction rate. This improves the leveling of the polyurea coating, facilitates the spreading of the polyurea over the first coating, enhances the adhesion of the polyurea coating to the first coating, and improves the long-term adhesion of the coating composition, allowing the polyurea coating to fully demonstrate its scratch and wear resistance. Furthermore, the ether bonds in the aromatic primary-terminated and secondary-terminated amino polyethers enhance the flexibility of the polymer chain segments. Furthermore, the diamine compound acts as a chain extender, promoting high molecular weight polyurea and improving the mechanical strength of the polyurea coating.

[0009] In any embodiment, the mass ratio of the aromatic primary amino-terminated polyether, the diamine compound and the secondary amino-terminated polyether in the first component is (6-8):(1-2):(1-3).

[0010] By controlling the mass ratio of the aromatic terminal primary amino polyether, the diamine compound, and the terminal secondary amino polyether in the first component within a suitable range, the reaction rate of the first component and the second component can be regulated within a suitable range, thereby improving the leveling property of the polyurea coating, improving the adhesion of the polyurea coating to the first coating, and improving the long-term adhesion of the coating composition. At the same time, it can also prevent the reaction rate from being too slow, which may affect the processing efficiency of the coating.

[0011] In any embodiment, the aromatic isocyanate compound in the second component includes an aromatic isocyanate prepolymer and an aromatic diisocyanate.

[0012] The aromatic diisocyanate reacts with the amino compound in the first component at a faster rate, which is beneficial to increasing the reaction rate of the polyurea coating. At the same time, the aromatic isocyanate prepolymer can provide flexible segments, improve the flexibility of the polyurea coating, and help improve the adhesion of the polyurea coating.

[0013] In any embodiment, the mass ratio of the aromatic isocyanate prepolymer to the aromatic diisocyanate in the second component is (2-8):(8-2).

[0014] By controlling the mass ratio of the aromatic isocyanate prepolymer to the aromatic diisocyanate in the second component within an appropriate range, the reaction rate and flexibility of the polyurea coating can be taken into account, as well as the processing performance and performance of the polyurea coating.

[0015] In any embodiment, the aromatic primary amino-terminated polyether includes one or both of poly-1,4-butylene glycol bis(4-aminobenzoate) and 4,4'-diaminodiphenyl ether.

[0016] In any embodiment, the secondary amino-terminated polyether includes one or both of di-secondary amino polyoxypropylene ether and 4-4'-di-sec-butylaminodiphenylmethane.

[0017] In any embodiment, the diamine compound includes one or more of 2,4'-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, N,N'-dialkylmethyldiamine, diaminodiphenylmethane, isophoronediamine, methyldiethanolamine, diacetylethylenediamine, dialkyltoluenediamine, 1,4-bis-sec-butylaminobenzene, bis-sec-butylaminodiphenylmethane, and N,N'-bis-pentylcyclohexanediamine.

[0018] In any embodiment, the aromatic isocyanate prepolymer includes one or more of polymethylene polyphenyl polyisocyanate prepolymer, diphenylmethane diisocyanate prepolymer, carbodiimide-modified diphenylmethane diisocyanate prepolymer, toluene diisocyanate prepolymer, xylene diisocyanate prepolymer, phenylene diisocyanate prepolymer, and dimethoxyaniline isocyanate prepolymer.

[0019] In any embodiment, the aromatic diisocyanate includes one or more of polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanate, and dimethoxyaniline isocyanate.

[0020] In any embodiment, the first coating further comprises a first filler, and the first filler comprises one or more of zinc powder, aluminum powder, glass fiber, and carbon fiber.

[0021] Zinc powder is added to the first coating. The standard potential of zinc is lower than that of steel. When the corrosive medium penetrates, the outer hull of the ship and the zinc powder form a primary battery. The zinc powder loses electrons as the negative electrode of the primary battery, and the outer hull of the ship gains electrons as the positive electrode and is protected.

[0022] Aluminum powder is added to the first coating, and each piece of aluminum powder can be overlapped in the coating, which is beneficial for the coating to shield the penetration and erosion of water vapor or other corrosive substances to the coating, and can also improve the wear resistance of the coating to achieve the purpose of long-term corrosion protection.

[0023] Adding glass fiber or carbon fiber to the first coating can increase the modulus and strength of the coating, which is beneficial to improving the scratch and wear resistance of the coating and achieving the purpose of long-term corrosion protection.

[0024] In any embodiment, the first component further comprises an aminosilane coupling agent.

[0025] The amino group at one end of the aminosilane coupling agent in the first component can react with the isocyanate group in the polyurea layer, and the silanol formed after the hydrolysis of the hydrolyzed group at the other end can react with the hydroxyl group in the side chain of the epoxy polymer or with the hydroxyl group on the surface of the zinc powder, aluminum powder, glass fiber, and carbon fiber in the epoxy polymer coating. The polyurea coating and the epoxy polymer coating are connected by chemical bonds, thereby improving the bonding strength between the layers and the adhesion between the coatings, thereby achieving the purpose of long-term corrosion protection.

[0026] In any embodiment, based on the total mass of the aromatic primary amino-terminated polyether, the diamine compound and the secondary amino-terminated polyether, the mass percentage of the aminosilane coupling agent is 0.2%-2.0%.

[0027] When the mass percentage of the aminosilane coupling agent is within an appropriate range, the purpose of chemically connecting the polyurea coating and the epoxy polymer coating can be achieved, while also preventing excessive aminosilane coupling agent from affecting the performance of the polyurea coating.

[0028] In any embodiment, the thickness of the first coating layer is 100 μm-150 μm.

[0029] In any embodiment, the thickness of the first coating layer is 110 μm-130 μm.

[0030] The thickness of the first coating is controlled within an appropriate range so that the first coating can completely cover the burrs and roughness on the outer hull of the ship, improve the flatness of the first coating, and facilitate the subsequent spreading of the second coating on the first coating. At the same time, the impact of excessive coating thickness on the exhaust velocity of the coating is reduced, the density of the coating is improved, and the purpose of long-term corrosion protection is achieved.

[0031] In any embodiment, the second coating layer has a thickness of 1000 μm to 10000 μm.

[0032] In any embodiment, the thickness of the second coating layer is 1500 μm to 3500 μm.

[0033] The thickness of the second coating is within an appropriate range, which is conducive to having sufficient time for the first component and the second component to spread on the first coating and react on the surface of the first coating to form a complete, uniform and dense polyurea layer. It also avoids the phenomenon that excessive heat caused by excessive thickness of the coating causes greater stress in the inner coating and the edge coating.

[0034] In any embodiment, the thickness of the third coating layer is 50 μm-150 μm.

[0035] In any embodiment, the thickness of the third coating layer is 80 μm-100 μm.

[0036] The thickness of the third coating is within an appropriate range, so that the third coating can cover the rough structure of the polyurea coating surface caused by rapid solidification and condensation to the greatest extent, improve the flatness, uniformity and density of the entire coating, and at the same time reduce the impact of excessive coating thickness on the exhaust speed of the coating, improve the density of the coating, and achieve the purpose of long-term corrosion protection.

[0037] A second aspect of the present application provides a use of a coating composition in a ship.

[0038] A third aspect of the present application provides a ship, comprising an outer hull and a coating composition at least partially disposed on a surface of the outer hull, wherein the coating composition is the coating composition described in the first aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Schematic diagram of an isolation membrane according to one embodiment of the present application.

[0040] Description of reference numerals:

[0041] 10 coating composition; 101 first coating layer; 102 second coating layer; 103 third coating layer. DETAILED DESCRIPTION

[0042] The coating composition, its applications, and embodiments of the vessel disclosed herein are described in detail below, with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of substantially identical structures may be omitted. This is to avoid unnecessary redundancy in the following description and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to facilitate a thorough understanding of the present application by those skilled in the art and are not intended to limit the subject matter recited in the claims.

[0043] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0044] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0045] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0046] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0047] Unless otherwise specified, the terms "include" and "comprising" used in this application may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0048] Unless otherwise specified, the term "or" is used in this application to be inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied if any of the following conditions are met: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0049] In order to improve the corrosion resistance of the outer hull of a ship, a protective layer is applied to the outer hull surface in the prior art. However, since the protective layer has no scratch and wear resistance, the ship often scrapes against the dock or the rubber fender on the dock during docking, causing the paint layer of the outer hull to wear out. Seawater can easily penetrate through the damaged coating. Under the conditions of capillary action and the secretion of corrosive substances by microorganisms, the aging and peeling of the protective layer are further accelerated, and the purpose of long-term corrosion protection cannot be achieved.

[0050] [Coating composition]

[0051] Figure 1 1 is a schematic diagram of an embodiment of the coating composition of the present application, wherein the coating composition 10 comprises a first coating 101, a second coating 102 located on the surface of the first coating 101, and a third coating 103 located on the surface of the second coating 102, wherein the first coating 101 comprises an epoxy polymer, the second coating 102 comprises an aromatic polyurea, and the third coating 103 comprises an aliphatic polyurethane, wherein the side chains of the epoxy polymer comprise hydroxyl groups.

[0052] As used herein, the term "epoxy polymer" refers to a polymer formed by cross-linking an epoxy resin with an amine compound.

[0053] As used herein, the term "aromatic polyurea" refers to a polymer having a urea group in the main chain and a benzene ring structure.

[0054] As used herein, the term "aliphatic polyurethane" refers to a polymer having a main chain containing -NH-COO- groups and not containing a benzene ring structure.

[0055] The first coating layer comprising epoxy polymer has good bonding strength with the outer hull of the ship, so that the coating composition can be permanently attached to the outer hull. At the same time, the side chain group hydroxyl group of the epoxy polymer can also react and combine with the isocyanate group of the aromatic polyurea in the second coating layer, so that the first coating layer and the second coating layer have excellent adhesion and can also improve the long-term adhesion of the second coating layer; the second coating layer comprising aromatic polyurea has excellent scratch and wear resistance, reducing the damage of the coating composition caused by scratches on the outer hull. At the same time, the high cross-linking density of the aromatic polyurea itself can effectively reduce the penetration and swelling of small molecules, reduce the corrosion effect of corrosive substances in seawater on the outer hull, and improve the anti-corrosion effect of the coating composition; the aliphatic polyurethane in the third coating layer mainly functions to improve the aging and yellowing resistance of the coating composition. At the same time, the hydroxyl group and isocyanate group in the aliphatic polyurethane can undergo cross-linking reaction with the isocyanate group and amine group in the polyurea to form good bonding strength, thereby improving the adhesion of the coating.

[0056] In summary, the coating composition of the present application includes three layers of coating, and the polymers in each coating are matched with each other to improve the long-term adhesion of the coating composition to the outer hull, improve the corrosion resistance, scratch resistance, wear resistance, yellowing resistance and aging resistance of the coating composition, and extend the service performance of the outer hull of the ship.

[0057] In some embodiments, the aromatic polyurea is formed by polymerizing a first component and a second component, wherein the first component comprises an aromatic primary amino-terminated polyether, a diamine compound, and a secondary amino-terminated polyether; and the second component comprises an aromatic isocyanate compound.

[0058] As used herein, the term "aromatic terminated primary amino polyether" refers to a polyoxyalkylene polymer terminated by a primary amino group, and the main chain of which contains a benzene ring structure.

[0059] Herein, the term "diamine compound" refers to a compound including two amino groups.

[0060] As used herein, the term "secondary amino-terminated polyether" refers to a polyoxyalkylene polymer terminated with a secondary amino group.

[0061] As used herein, the term "aromatic isocyanate compound" refers to a compound having a main chain including an isocyanate group and a benzene ring structure.

[0062] Aromatic polyureas are produced by the reaction of an aromatic isocyanate compound (a second component) with an amino compound (a first component). The amino compound (a first component) contains both primary-terminated and secondary-terminated amino polyethers, which can regulate the reaction rate between the amino group and the isocyanate, achieving a moderate reaction rate. This improves the leveling of the polyurea coating, facilitates the spreading of the polyurea over the first coating, enhances the adhesion of the polyurea coating to the first coating, and improves the long-term adhesion of the coating composition, allowing the polyurea coating to fully demonstrate its scratch and wear resistance. Furthermore, the ether bonds in the aromatic primary-terminated and secondary-terminated amino polyethers enhance the flexibility of the polymer chain segments. Furthermore, the diamine compound acts as a chain extender, promoting high molecular weight polyurea and improving the mechanical strength of the polyurea coating.

[0063] In some embodiments, the mass ratio of the aromatic primary amino-terminated polyether, the diamine compound, and the secondary amino-terminated polyether in the first component is (6-8):(1-2):(1-3).

[0064] In some embodiments, the mass ratio of the aromatic primary amino-terminated polyether, the diamine compound and the secondary amino-terminated polyether in the first component can be 6:2:2, 6:1:3, 7:1:2, 7:2:1, 8:1:1 or any range therebetween.

[0065] By controlling the mass ratio of the aromatic terminal primary amino polyether, the diamine compound, and the terminal secondary amino polyether in the first component within a suitable range, the reaction rate of the first component and the second component can be regulated within a suitable range, thereby improving the leveling property of the polyurea coating, improving the adhesion of the polyurea coating to the first coating, and improving the long-term adhesion of the coating composition. At the same time, it can also prevent the reaction rate from being too slow, which may affect the processing efficiency of the coating.

[0066] In some embodiments, the aromatic isocyanate compound in the second component includes an aromatic isocyanate prepolymer and an aromatic diisocyanate.

[0067] As used herein, the term "aromatic isocyanate prepolymer" refers to a polymer formed by reacting an excess of aromatic diisocyanate with a polyether diol or polyester diol.

[0068] As used herein, the term "aromatic diisocyanate" refers to a compound whose main chain includes a -N=C=O group and a benzene ring structure.

[0069] The aromatic diisocyanate reacts with the amino compound in the first component at a faster rate, which is beneficial to increasing the reaction rate of the polyurea coating. At the same time, the aromatic isocyanate prepolymer can provide flexible segments, improve the flexibility of the polyurea coating, and help improve the adhesion of the polyurea coating.

[0070] In some embodiments, the mass ratio of the aromatic isocyanate prepolymer to the aromatic diisocyanate in the second component is (2-8):(8-2). In some embodiments, the mass ratio of the aromatic isocyanate prepolymer to the aromatic diisocyanate in the second component can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 3:7, or any range therebetween.

[0071] By controlling the mass ratio of the aromatic isocyanate prepolymer to the aromatic diisocyanate in the second component within an appropriate range, the reaction rate and flexibility of the polyurea coating can be taken into account, as well as the processing performance and performance of the polyurea coating.

[0072] In some embodiments, the aromatic primary amino-terminated polyether includes one or both of poly-1,4-butylene glycol bis(4-aminobenzoate) and 4,4'-diaminodiphenyl ether.

[0073] In some embodiments, the secondary amino-terminated polyether includes one or more of di-secondary amino polyoxypropylene ether and 4-4'-di-sec-butylaminodiphenylmethane.

[0074] In some embodiments, the diamine compound includes one or more of 2,4'-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, N,N'-dialkylmethyldiamine, diaminodiphenylmethane, isophoronediamine, methyldiethanolamine, diacetylethylenediamine, dialkyltoluenediamine, 1,4-bis-sec-butylaminobenzene, bis-sec-butylaminodiphenylmethane, and N,N'-bis-pentylcyclohexanediamine.

[0075] In some embodiments, the aromatic isocyanate prepolymer includes one or more of polymethylene polyphenyl polyisocyanate prepolymer, diphenylmethane diisocyanate prepolymer, carbodiimide-modified diphenylmethane diisocyanate prepolymer, toluene diisocyanate prepolymer, xylene diisocyanate prepolymer, phenylene diisocyanate prepolymer, and dimethoxyaniline isocyanate prepolymer.

[0076] In some embodiments, the aromatic diisocyanate includes one or more of polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanate, and dimethoxyaniline isocyanate.

[0077] In some embodiments, the first coating further comprises a first filler, and the first filler comprises one or more of zinc powder, aluminum powder, glass fiber, and carbon fiber.

[0078] Zinc powder is added to the first coating. The standard potential of zinc is lower than that of steel. When the corrosive medium penetrates, the outer hull of the ship and the zinc powder form a primary battery. The zinc powder loses electrons as the negative electrode of the primary battery, and the outer hull of the ship gains electrons as the positive electrode and is protected, thereby improving the anti-corrosion performance of the coating.

[0079] Aluminum powder is added to the first coating, and each piece of aluminum powder can be overlapped in the coating, which is beneficial for the coating to shield the penetration and erosion of water vapor or other corrosive substances to the coating, and can also improve the wear resistance of the coating and improve the anti-corrosion performance of the coating.

[0080] Adding glass fiber or carbon fiber to the first coating can increase the modulus and strength of the coating, which is beneficial to improving the scratch and wear resistance of the coating and improving the corrosion resistance of the coating.

[0081] In some embodiments, the first component further comprises an aminosilane coupling agent.

[0082] In some embodiments, the aminosilane coupling agent includes one or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldiethoxysilane, anilinomethyltriethoxysilane, anilinomethyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane.

[0083] As mentioned above, adding zinc powder, aluminum powder, glass fiber or carbon fiber to the first coating can improve the corrosion resistance of the coating. However, adding zinc powder, aluminum powder, glass fiber or carbon fiber to the first coating will affect the bonding and adhesion between the epoxy polymer coating and the polyurea coating, affecting the long-term adhesion performance of the coating.

[0084] The present application adds an aminosilane coupling agent to the first component. The amino group at one end of the aminosilane coupling agent in the first component can react with the isocyanate group in the polyurea layer. The silanol formed after the hydrolysis of the hydrolyzed group at the other end can react with the hydroxyl group in the side chain of the epoxy polymer or with the hydroxyl group on the surface of the zinc powder, aluminum powder, glass fiber, and carbon fiber in the epoxy polymer coating. The polyurea coating and the epoxy polymer coating are connected by chemical bonds, thereby improving the bonding strength between the layers and the adhesion between the coatings, thereby achieving the purpose of long-term corrosion protection.

[0085] In some embodiments, the mass percentage of the aminosilane coupling agent is 0.2%-2.0% based on the total mass of the aromatic primary amino-terminated polyether, the diamine compound, and the secondary amino-terminated polyether. In some embodiments, the mass percentage of the aminosilane coupling agent is 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, or any range therebetween, based on the total mass of the aromatic primary amino-terminated polyether, the diamine compound, and the secondary amino-terminated polyether.

[0086] When the mass percentage of the aminosilane coupling agent is within an appropriate range, the purpose of chemically connecting the polyurea coating and the epoxy polymer coating can be achieved, while also preventing excessive aminosilane coupling agent from affecting the performance of the polyurea coating.

[0087] In some embodiments, the thickness of the first coating layer is 100 μm-150 μm, optionally 110 μm-130 μm.

[0088] In some embodiments, the thickness of the first coating layer may be 100 μm, 110 μm, 120 μm, 140 μm, 150 μm, or any range therebetween.

[0089] The thickness of the first coating is controlled within an appropriate range so that the first coating can completely cover the burrs and roughness on the outer hull of the ship, improve the flatness of the first coating, and facilitate the subsequent spreading of the second coating on the first coating. At the same time, the impact of excessive coating thickness on the exhaust velocity of the coating is reduced, the density of the coating is improved, and the purpose of long-term corrosion protection is achieved.

[0090] In some embodiments, the second coating layer has a thickness of 1000 μm-10000 μm, optionally 1500 μm-3500 μm.

[0091] In some embodiments, the thickness of the second coating layer may be selected from 1000 μm to 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm, 5500 μm, 6000 μm, 6500 μm, 7000 μm, 7500 μm, 8000 μm, 8500 μm, 9000 μm, 9500 μm, 10000 μm, or any range therebetween.

[0092] The thickness of the second coating is within an appropriate range, which is conducive to having sufficient time for the first component and the second component to spread on the first coating and react on the surface of the first coating to form a complete, uniform and dense polyurea layer. It also avoids the phenomenon that excessive heat caused by excessive thickness of the coating causes greater stress in the inner coating and the edge coating.

[0093] In some embodiments, the thickness of the third coating layer is 50 μm-150 μm, optionally 80 μm-100 μm.

[0094] In some embodiments, the thickness of the third coating layer may be 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or any range therebetween.

[0095] The thickness of the third coating is within an appropriate range, so that the third coating can cover the rough structure of the polyurea coating surface caused by rapid solidification and condensation to the greatest extent, improve the flatness, uniformity and density of the entire coating, and at the same time reduce the impact of excessive coating thickness on the exhaust speed of the coating, improve the density of the coating, and achieve the purpose of long-term corrosion protection.

[0096] The present application also provides use of the coating composition in any embodiment in a ship.

[0097] The present application also provides a ship, comprising an outer hull and a coating composition at least partially disposed on a surface of the outer hull, wherein the coating composition is as described in any embodiment.

[0098] Example

[0099] Below, the embodiment of the present application is described. The embodiment described below is exemplary and is only used to explain the present application, and is not to be construed as limiting the present application. Where specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used that do not specify the manufacturer are conventional products that can be obtained commercially.

[0100] 1. Preparation method

[0101] Example 1

[0102] 1) Coating composition

[0103] First coating preparation method:

[0104] An epoxy primer (Hempel 17720) was applied to the steel substrate and cured at room temperature for 12 hours to form a first coating with a thickness of 120 μm.

[0105] Poly-1,4-butanediol bis(4-aminobenzoate) and 2,4'-diaminodiphenylmethane are prepared in a mass ratio of 9:1 to form a first component; diphenylmethane diisocyanate prepolymer and diphenylmethane diisocyanate are prepared in a mass ratio of 2:8 to form a second component, wherein the diphenylmethane diisocyanate prepolymer is formed by polymerizing diphenylmethane diisocyanate and diamino-terminated polyoxyethylene ether in a molar ratio of 1.1:1; the first component and the second component are respectively loaded into a raw material barrel of a sprayer, heated separately, mixed, and subjected to high-pressure atomization, and sprayed onto the surface of the first coating to form a second coating with a thickness of 2000 μm;

[0106] Aliphatic polyurethane (Hempel's polyurethane topcoat 55610) was brush-coated on the surface of the second coating layer and cured at room temperature for 12 hours to form a third coating layer with a thickness of 90 μm, thereby obtaining a sample panel.

[0107] Example 2

[0108] Compared with Example 1, Example 2 adjusts the preparation method of the second coating layer, specifically as follows:

[0109] Poly-1,4-butanediol bis(4-aminobenzoate), 2,4'-diaminodiphenylmethane, and di-secondary amino polyoxypropylene ether are prepared in a mass ratio of 7:1:2 to form a first component; diphenylmethane diisocyanate prepolymer and diphenylmethane diisocyanate are prepared in a mass ratio of 2:8 to form a second component, wherein the diphenylmethane diisocyanate prepolymer is formed by polymerizing diphenylmethane diisocyanate and diamino-terminated polyoxyethylene ether in a molar ratio of 1.1:1); the first component and the second component are respectively loaded into the raw material barrel of a sprayer, first heated separately, then mixed and subjected to high-pressure atomization, and sprayed onto the surface of the first coating to form a second coating with a thickness of 2000 μm.

[0110] Example 3

[0111] Compared with Example 2, in Example 3, the di-secondary amino polyoxypropylene ether is replaced with 4-4'-di-secondary butylaminodiphenylmethane. For specific parameters, see Table 1.

[0112] Examples 4-7

[0113] Compared with Example 2, Examples 4-7 adjusted the mass ratios of poly-1,4-butanediol bis(4-aminobenzoate), 2,4'-diaminodiphenylmethane, and bis(amino)polyoxypropylene ether in the first component. For specific parameters, see Table 1.

[0114] Example 8

[0115] Compared with Example 2, the epoxy primer was replaced with an epoxy primer containing zinc filler (Hempel zinc-rich primer 15341).

[0116] Example 9

[0117] Compared with Example 8, the preparation method of the second coating layer was adjusted as follows:

[0118] Poly-1,4-butanediol bis(4-aminobenzoate), 2,4'-diaminodiphenylmethane, and di-secondary amino polyoxypropylene ether are mixed in a mass ratio of 7:1:2, and a methyltriethoxysilane coupling agent accounting for 0.5% of the mass fraction of the mixture is added to obtain a first component; diphenylmethane diisocyanate prepolymer and diphenylmethane diisocyanate are mixed in a mass ratio of 2:8 to form a first component, wherein the diphenylmethane diisocyanate prepolymer is formed by polymerizing diphenylmethane diisocyanate and diamino-terminated polyoxyethylene ether in a molar ratio of 1.1:1. The first component and the second component are respectively loaded into the raw material barrel of a sprayer, first heated separately, then mixed and subjected to high-pressure atomization, and sprayed onto the surface of the first coating to form a second coating with a thickness of 2000 μm.

[0119] Example 10

[0120] Compared with Example 9, the methyltriethoxysilane coupling agent was replaced with γ-aminopropyltriethoxysilane. For specific parameters, see Table 1.

[0121] Comparative Example 1

[0122] Compared with Example 1, the preparation method of the second coating layer was adjusted as follows:

[0123] A first component is formed by combining diamino-terminated polyoxypropylene ether and diamino-terminated polyoxyethylene ether in a mass ratio of 8:2; a second component is formed by combining isophorone diisocyanate prepolymer and isophorone diisocyanate in a mass ratio of 2:8, wherein the isophorone isocyanate prepolymer is formed by polymerizing isophorone diisocyanate and diamino-terminated polyoxyethylene ether in a molar ratio of 1.1:1. The first component and the second component are respectively loaded into a raw material barrel of a sprayer, heated separately, mixed, and subjected to high-pressure atomization, and sprayed onto the surface of the first coating to form a second coating with a thickness of 2000 μm.

[0124] Comparative Example 2

[0125] Compared to Example 1, the application of the second coating polyurea layer was not performed.

[0126] Comparative Example 3

[0127] Compared to Example 1, the application of the third coating polyurethane layer was not performed.

[0128] 2. Test Method

[0129] 1. Anti-corrosion testing of coating compositions under extreme environments

[0130] The coating composition is subjected to a wear resistance test, an impact resistance test, a hot salt water resistance test and a salt spray resistance test in sequence to obtain the test results of the coating composition's anti-corrosion, anti-scratch and wear resistance.

[0131] Wear resistance test: Referring to GB / T 1768-2006 standard, the wear resistance test was conducted using friction medium CS-17 with a load of 1000g and a rotation speed of 67r / min on the test sample for 50,000 revolutions.

[0132] Impact resistance performance test: Refer to GB / T 20624.1-2006 standard, the ball head diameter is 20mm, the weight of the hammer is 20kg, and the falling height of the hammer is 1m.

[0133] Hot salt water resistance test: Refer to GB / T 10834-2008 standard, the test period is 42 days.

[0134] Salt spray resistance test: Refer to GB / T 1771-2007 standard, no scratch test, test cycle is 1000h.

[0135] 2. UV aging resistance test of coating composition

[0136] The surface chromaticity of the intact part of the paint film in the test sample that has undergone the above-mentioned abrasion resistance test, impact resistance test, hot salt water resistance test and salt spray resistance test in sequence according to ISO 7724-2 is recorded as E0;

[0137] According to the UVA-340 requirements of ISO 4892-3, the intact part of the test sample that has undergone the above-mentioned abrasion resistance test, impact resistance test, hot salt water resistance test and salt spray resistance test is subjected to UV aging test. The irradiance parameter at 340nm is: 0.76W / m 2 , number of test lamps: 8 lamps, test time: 1000h; test the surface chromaticity of the paint film of the sample after the UV aging test in accordance with ISO 7724-2, recorded as E1;

[0138] Calculate the color difference before and after the test ⊿E=E1-E0.

[0139] 3. Adhesion test of the coating composition after double 85 aging

[0140] An aging test chamber was used, the temperature was maintained at 85° C., the relative humidity was maintained at 85%, and the coating compositions of the examples and comparative examples, after being cured at room temperature for 7 days, were placed in the aging chamber and aged for 1000 hours to obtain test samples;

[0141] The adhesion test method of the coating composition refers to GB / T 5210-2006 "Paints and varnishes - adhesion test by pull-off method", and the adhesion between the coating composition and the steel substrate surface is tested by a tensile test method.

[0142] 3. Analysis of test results of various embodiments and comparative examples

[0143] The coating compositions of the examples and comparative examples were prepared according to the above methods, and various parameters were measured. The results are shown in the table below.

[0144] Table 1

[0145]

[0146]

[0147] Note: The reason why comparative examples 1 and 2 were not subjected to UV aging resistance test is that after the previous corrosion resistance test, most of the test samples were corroded and destroyed, and there was no need to conduct aging resistance test.

[0148] The coating compositions in Examples 1-10 of the present application comprise a first coating layer, a second coating layer located on the surface of the first coating layer, and a third coating layer located on the surface of the second coating layer, wherein the first coating layer comprises an epoxy polymer, the second coating layer comprises an aromatic polyurea, and the third coating layer comprises an aliphatic polyurethane.

[0149] From the comparison of Examples 1-10 and Comparative Example 1, it can be seen that compared with the coating composition using aliphatic polyurea as the second coating layer, the coating composition of the present application can improve the anti-corrosion effect of the coating composition in extreme environments.

[0150] From the comparison of Examples 1-10 and Comparative Example 2, it can be seen that compared with the coating composition of the second coating layer not comprising polyurea, the coating composition of the present application can improve the anti-corrosion effect of the coating composition in extreme environments.

[0151] From the comparison of Examples 1-10 and Comparative Example 3, it can be seen that compared with the coating composition of the third coating layer that does not contain aliphatic polyurethane, the coating composition of the present application can improve the light aging resistance of the coating and reduce the color difference of the coating under the action of light.

[0152] Table 2

[0153] Serial number Adhesion testing of coating compositions Example 1 9.6MPa, the interface between the first coating and the second coating is mainly damaged Example 2 15.1MPa, mainly the interface between the first coating and the substrate is damaged Example 3 16.1MPa, mainly the interface between the first coating and the substrate is damaged Example 4 15.9MPa, mainly the interface between the first coating and the substrate is damaged Example 5 15.2MPa, mainly the interface between the first coating and the substrate is damaged Example 6 15.5MPa, mainly the interface between the first coating and the substrate is damaged Example 7 15.7MPa, mainly the interface between the first coating and the substrate is damaged Example 8 12.3MPa, the interface between the first coating and the second coating is mainly damaged Example 9 12.3MPa, interface between polyurea coating and epoxy coating is damaged Example 10 15.7MPa, mainly the interface between the first coating and the substrate is damaged

[0154] From the comparison between Examples 2-7 and Example 1, it can be seen that the first component used for the aromatic polyurea includes terminal secondary amino polyether, which improves the adhesion between the coating composition and the substrate and achieves the purpose of long-term corrosion protection.

[0155] It can be seen from Examples 2-7 that when the mass ratio of the aromatic terminal primary amino polyether, the diamine compound and the terminal secondary amino polyether in the first component is (6-8):(1-2):(1-3), the coating composition has excellent anti-corrosion effect under extreme environments, and the coating composition has good long-term adhesion performance, which can achieve the purpose of long-term anti-corrosion.

[0156] From the comparison between Example 10 and Examples 8-9, it can be seen that adding an aminosilane coupling agent to the second coating layer can significantly improve the long-term adhesion performance of the coating composition and extend the service life of the coating composition.

[0157] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A coating composition, characterized in that comprising a first coating layer, a second coating layer located on a surface of the first coating layer, and a third coating layer located on a surface of the second coating layer, The first coating layer comprises an epoxy polymer, the second coating layer comprises an aromatic polyurea, and the third coating layer comprises an aliphatic polyurethane, wherein the side chain of the epoxy polymer comprises a hydroxyl group.

2. The coating composition according to claim 1, wherein The aromatic polyurea is formed by polymerizing a first component and a second component, wherein the first component comprises an aromatic primary amino-terminated polyether, a diamine compound, and a secondary amino-terminated polyether; and the second component comprises an aromatic isocyanate compound.

3. The coating composition according to claim 2, characterized in that The mass ratio of the aromatic primary amino-terminated polyether, the diamine compound and the secondary amino-terminated polyether in the first component is (6-8):(1-2):(1-3).

4. The coating composition according to claim 2 or 3, characterized in that The aromatic isocyanate compound in the second component includes aromatic isocyanate prepolymer and aromatic diisocyanate.

5. The coating composition according to claim 4, characterized in that The mass ratio of the aromatic isocyanate prepolymer to the aromatic diisocyanate in the second component is (2-8):(8-2).

6. The coating composition according to any one of claims 2 to 5, characterized in that The aromatic primary amino-terminated polyether includes one or both of poly-1,4-butylene glycol bis(4-aminobenzoate) and 4,4'-diaminodiphenyl ether.

7. The coating composition according to any one of claims 2 to 6, characterized in that The secondary amino-terminated polyether includes one or two of di-secondary amino polyoxypropylene ether and 4-4'-di-secondary butylaminodiphenylmethane.

8. The coating composition according to any one of claims 2 to 7, characterized in that The diamine compound includes one or more of 2,4'-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, N,N'-dialkylmethyldiamine, diaminodiphenylmethane, isophoronediamine, methyldiethanolamine, diacetylethylenediamine, dialkyltoluenediamine, 1,4-bis-sec-butylaminobenzene, bis-sec-butylaminodiphenylmethane, and N,N'-bis-pentylcyclohexanediamine.

9. The coating composition according to any one of claims 4 to 8, characterized in that The aromatic isocyanate prepolymer includes one or more of polymethylene polyphenyl polyisocyanate prepolymer, diphenylmethane diisocyanate prepolymer, carbodiimide-modified diphenylmethane diisocyanate prepolymer, toluene diisocyanate prepolymer, xylene diisocyanate prepolymer, phenylene diisocyanate prepolymer, and dimethoxyaniline isocyanate prepolymer.

10. The coating composition according to any one of claims 4 to 9, characterized in that The aromatic diisocyanate includes one or more of polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanate, and dimethoxyaniline isocyanate.

11. The coating composition according to any one of claims 1 to 10, characterized in that The first coating layer further comprises a first filler, and the first filler comprises one or more of zinc powder, aluminum powder, glass fiber, and carbon fiber.

12. The coating composition according to any one of claims 2 to 11, characterized in that The first component also includes an aminosilane coupling agent.

13. The coating composition according to claim 12, characterized in that Based on the total mass of the aromatic primary amino-terminated polyether, the diamine compound and the secondary amino-terminated polyether, the mass percentage of the aminosilane coupling agent is 0.2%-2.0%.

14. The coating composition according to any one of claims 1 to 13, characterized in that The thickness of the first coating layer is 100 μm-150 μm.

15. The coating composition according to any one of claims 1 to 13, characterized in that The thickness of the first coating layer is 110 μm-130 μm.

16. The coating composition according to any one of claims 1 to 15, characterized in that The thickness of the second coating layer is 1000 μm-10000 μm.

17. The coating composition according to any one of claims 1 to 15, characterized in that The thickness of the second coating layer is 1500 μm-3500 μm.

18. The coating composition according to any one of claims 1 to 17, characterized in that The thickness of the third coating layer is 50 μm-150 μm.

19. The coating composition according to any one of claims 1 to 17, characterized in that The thickness of the third coating layer is 80 μm-100 μm.

20. Use of the coating composition according to any one of claims 1 to 19 in ships.

21. A ship, characterized in that: The invention comprises an outer hull and a coating composition at least partially disposed on a surface of the outer hull, wherein the coating composition is the coating composition according to any one of claims 1 to 19.

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