An epoxy tiecoat for marine vessels and a method of making the same

Abstract

The present application relates to the field of paint, in particular to a kind of epoxy connection paint for ship and preparation method thereof.The epoxy connection paint for ship, component A includes: epoxy resin A 15-30 parts, epoxy resin B 10-15 parts, wetting dispersant 0.1-1.5 parts, anti-settling agent 0.5-5 parts, defoaming agent 0.1-0.2 parts, pigment 15-20 parts, filler 25-30 parts, adhesion promoter 0.5-1.5 parts, first solvent 25-40 parts;The epoxy resin B includes cashew phenol-based epoxy resin and methoxy polyethylene glycol;The adhesion promoter includes silane coupling agent, polydopamine and polycaprolactone;The anti-settling agent includes epoxy-based POSS and polyamide wax;The wetting dispersant includes oleylamine and polybutyl acrylate;Component B includes: modified amine curing agent 80-90 parts, epoxy promoter 1-5 parts, second solvent 5-10 parts;The component A and component B are mixed according to weight ratio (10-15):1.The epoxy connection paint for ship of the present application has the performance of higher adhesion, stronger corrosion resistance, stronger antifouling property and long-term stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of paint, in particular to an epoxy tie coat for ships and a preparation method thereof. BACKGROUND

[0002] As a key transition layer of ship antifouling coating system, the epoxy tie coat not only needs to provide a good adhesion base for the topcoat, but also needs to play the role of "the second line of defense" when the antifouling paint is damaged or fails. However, in practical application, the tie coat still has many performance defects: in terms of adhesion, the adhesion of the tie coat to the antifouling topcoat and the epoxy anticorrosive primer is insufficient, the interfacial bonding strength is low, and the coating is easy to peel off due to seawater erosion or ship vibration; in terms of antifouling performance, it completely depends on the protection of the antifouling topcoat, and once the antifouling topcoat is damaged, biological fouling will directly erode the coating; in terms of corrosion resistance, although the antifouling topcoat has a certain barrier effect, it is difficult to resist the penetration of corrosive media for a long time, and the coating is easy to appear blistering and powdering phenomenon; due to the poor compatibility of the tie coat with different types of release type antifouling coatings, it is difficult to adapt to diversified antifouling coating systems, and problems such as interlayer repulsion and poor combination are easy to occur. Therefore, it is urgent to develop a tie coat that can simultaneously realize high adhesion, strong corrosion resistance, strong antifouling property and other properties, and meet the comprehensive performance requirements of the tie coat of the ship in the complex marine environment. SUMMARY

[0003] Therefore, the technical problem to be solved by the present application is to overcome the deficiencies and defects in the prior art, and to provide an epoxy tie coat for ships and a preparation method thereof, which can improve the adhesion, corrosion resistance, antifouling property and stability of the paint film.

[0004] In order to solve the above problems:

[0005] The present application provides an epoxy tie coat for ships, comprising component A and component B.

[0006] The component A comprises the following raw materials in parts by weight: epoxy resin A 15-30 parts, epoxy resin B 10-15 parts, wetting dispersant 0.1-1.5 parts, anti-settling agent 0.5-5 parts, defoaming agent 0.1-0.2 parts, pigment 15-20 parts, filler 25-30 parts, adhesion promoter 0.5-1.5 parts, and first solvent 25-40 parts.

[0007] The epoxy resin A is a bisphenol A type epoxy resin with an epoxy equivalent weight of 200-250 g / mol.

[0008] The epoxy resin B is compounded from cardanol-based epoxy resin and methoxy polyethylene glycol.

[0009] The component B comprises the following raw materials in parts by weight: modified amine curing agent 80-90 parts, epoxy promoter 1-5 parts, and second solvent 5-10 parts.

[0010] The A component and the B component are mixed in a weight ratio of (10-15):1.

[0011] Preferably, the adhesion promoter is compounded by a silane coupling agent, polydopamine and polycaprolactone.

[0012] Preferably, the anti-settling agent is compounded by epoxy POSS and polyamide wax.

[0013] Preferably, the wet dispersant is compounded by oleylamine and polybutyl acrylate.

[0014] Preferably, the weight ratio of the cardanol-based epoxy resin and methoxy polyethylene glycol is (4-14):1.

[0015] Further preferably, the weight ratio of the silane coupling agent, polydopamine and polycaprolactone is (2-5):(1-3):(2-7); the silane coupling agent is selected from one or more of Z-6026, SICO-A119 and SICO-A210.

[0016] Further preferably, the weight ratio of the epoxy POSS and polyamide wax is 1:(9-12); the epoxy POSS is selected from one or both of Ecotion POSS1010 and Ecotion® POSS101.

[0017] Further preferably, the weight ratio of the oleylamine and polybutyl acrylate is 1:(4-7).

[0018] Preferably, the bisphenol A type epoxy resin is selected from one or both of E-44 and E-51; the defoaming agent is a silicone-based defoaming agent, the silicone-based defoaming agent is selected from one or more of BYK-066N, BYK-141 and TEGO Foamex 810; the pigment is selected from one or more of iron red, titanium white powder and carbon black; the filler is selected from one or more of barium sulfate, mica powder and talc powder; the first solvent and the second solvent are both selected from one or more of dimethylbenzene, propylene glycol methyl ether acetate, diacetone alcohol, dimethyl carbonate and n-butanol; the modified amine curing agent is selected from one or more of EH-226A, Hensamine-4075 and ARADUR 283; the epoxy promoter is selected from one or both of YH5230 and DMP-30.

[0019] The application also provides a preparation method of the epoxy connection paint for ships, comprising the following preparation steps:

[0020] comprising the following steps:

[0021] S1: The first solvent, epoxy resin A and epoxy resin B are sequentially put into the dispersion kettle according to the predetermined weight parts, and dispersed for 30-60 minutes;

[0022] S2: The wetting dispersant and the defoaming agent are sequentially put into the dispersion kettle according to the predetermined weight parts, and dispersed for 10-30 minutes;

[0023] S3: The anti-settling agent and the adhesion promoter are sequentially put into the dispersion kettle according to the predetermined weight parts, and dispersed for 10-30 minutes, and the temperature is raised to 60-70 DEG C, and the temperature is kept for 30 minutes;

[0024] S4: The pigment and the filler are sequentially put into the dispersion kettle according to the predetermined weight parts, and high-speed dispersion is carried out for 30-60 minutes, and the grinding machine is transferred to grind to a fineness of less than or equal to 80 mu m;

[0025] S5: The viscosity is adjusted to 90-110 KU using the first solvent, and the A component is prepared by filtering and sealing;

[0026] S6: The modified amine curing agent, the epoxy promoter and the second solvent are sequentially put into the dispersion kettle according to the predetermined weight parts, and are uniformly stirred and dispersed for 15-30 minutes, and the B component is prepared by sealing;

[0027] S7: The A component and the B component are mixed uniformly according to the weight ratio (10-15): 1 to obtain the epoxy connection paint for ships.

[0028] The technical scheme of the present application has the following advantages:

[0029] 1. The epoxy resin B provided by the present application is compounded by cashew phenol-based epoxy resin and methoxy polyethylene glycol. The two have good complementarity in molecular configuration and conformational freedom, low steric hindrance effect between chain segments, and can synergistically act on polar and non-polar interfaces; the long alkyl chain segment of cashew phenol provides hydrophobicity, enhances the overall water resistance of the coating, the continuous -CH2- units and cis double bond structure in the carbon chain make it have a flexible structure, which helps to form a dense cross-linked network and improve the cohesive strength of the coating; methoxy polyethylene glycol is rich in ether bonds, which can provide hydrophilicity, one end of methoxy polyethylene glycol is inert methoxy, and the other end is hydroxyl which can react with epoxy group, compared with polyethylene glycol with hydroxyl groups at both ends, methoxy polyethylene glycol can form a more uniform network and stronger hydrolysis resistance with cashew phenol-based epoxy resin. At the same time, by adjusting the proportion of hydrophilic and hydrophobic chain segments, the hydrophilic and hydrophobic properties of the molecules can be balanced to ensure that the ether bonds of methoxy polyethylene glycol are exposed on the surface, thereby optimizing the adhesion of the coating to the substrate. In addition, the hydrophobic chain segment maintains the internal structure stability and hydrophobicity of the coating, and the hydrophilic chain segment can migrate to the coating-water interface in seawater to form a hydration layer, which prevents the attachment of fouling organisms through steric hindrance effect, thereby realizing the antifouling function.

[0030] 2. The adhesion promoter provided by the present application is compounded by silane coupling agent, polydopamine and polycaprolactone. The silane coupling agent forms a dense covalent bonding layer on the metal surface through reaction, the dopamine spontaneously polymerizes to form a dopamine layer under alkaline conditions, and the layer forms coordination bonds, hydrogen bonds and other non-covalent interactions with the metal surface through groups such as pyrocatechol, effectively covers the micro defects and enhances the surface wettability; at the same time, the active groups of polydopamine can further react with silane to form a dense and stable composite interface, which can block the penetration of water molecules and corrosive media, and to some extent, improve the corrosion resistance of the coating. At the same time, polycaprolactone introduces a flexible buffer phase into the interface layer through penetration or interface modification, the low rotational barrier of its carbon-carbon single bond makes its molecular chain have high flexibility, and its glass transition temperature is far lower than room temperature, so it can be in a high elastic state at room temperature, and it can absorb stress through conformational change, effectively improving the problem that the brittleness of the system may increase when silane coupling agent and polydopamine are compounded; when the interface is impacted, the rigid network of silane is responsible for maintaining the stability of the overall structure, the flexible segment of polycaprolactone absorbs energy through deformation, and the dynamic bond of polydopamine prevents the generation and expansion of cracks by virtue of its reversible breaking and recombination mechanism, ultimately improving the toughness and impact resistance of the system.

[0031] 3. The anti-settling agent provided by the present application is compounded by epoxy POSS and polyamide wax. Epoxy POSS is a cubic cage structure composed of siloxane bonds, which is close to the molecular chain spacing of polyamide wax and can be physically embedded in the network gap. After the embedding of POSS in the hydrogen bond network of polyamide wax, the network density is enhanced through molecular chain entanglement and chemical bonding, reducing the penetration of corrosive media and simultaneously improving the anti-settling and anti-corrosion performance; during the coating scraping and rolling process, under the action of shear force, the rigid structure of POSS can limit the disordered thermal motion of molecules, guiding the directional arrangement of polyamide wax, and reconfiguring the traditional hydrogen bond network formed by random collision into an efficient self-assembly system centered on POSS, significantly improving the viscosity of the system, effectively avoiding the delamination and caking caused by the settling of pigments and fillers, and improving the anti-sagging property and the gloss stability of the paint film.

[0032] 4. The wetting dispersant provided by the present application is compounded by oleylamine and polybutyl acrylate. Oleylamine prevents particle agglomeration through electrostatic repulsion and has rapid wetting ability, which can achieve the initial dispersion of pigment particles; polybutyl acrylate maintains long-term dispersion stability through steric hindrance effect, effectively avoiding the re-flocculation problem that may be caused by the use of oleylamine alone, thereby achieving the rapid and stable dispersion of pigment particles; in addition, the hydrophobic interaction between the long alkyl chain of oleylamine and polybutyl acrylate can inhibit the surface migration of oleylamine during the drying process, and the uniform surface tension characteristics of polybutyl acrylate reduce the surface tension gradient of the coating, thereby inhibiting defects such as shrinkage and pinholes. DETAILED DESCRIPTION

[0033] The following examples are provided to better further understand the present application and are not limited to the best mode contemplated, do not constitute a limitation of the content and scope of the present application, and any person skilled in the art under the guidance of the present application or the combination of the present application with other prior art features obtains any product identical or similar to the present application, which falls within the scope of the present application.

[0034] The specific experimental steps or conditions not mentioned in the examples can be carried out according to the conventional experimental steps or conditions described in the literature in the art. The reagents or instruments not mentioned by the manufacturer are conventional reagent products that can be obtained by purchase.

[0035] The epoxy connection paint for a ship provided by the present application comprises component A and component B; the component A comprises the following raw materials in parts by weight: epoxy resin A 15-30 parts, epoxy resin B 10-15 parts, wetting dispersant 0.1-1.5 parts, anti-settling agent 0.5-5 parts, defoaming agent 0.1-0.2 parts, pigment 15-20 parts, filler 25-30 parts, adhesion promoter 0.5-1.5 parts, and first solvent 25-40 parts; the component B comprises the following raw materials in parts by weight: modified amine curing agent 80-90 parts, epoxy promoter 1-5 parts, and second solvent 5-10 parts; and the component A and the component B are mixed in a weight ratio of (10-15) : 1.

[0036] In the present application, the epoxy resin B is compounded from cardanol-based epoxy resin and methoxy polyethylene glycol; the two molecular configurations and conformational freedom of the cardanol-based epoxy resin and the methoxy polyethylene glycol have good complementarity, the steric hindrance effect between the chain segments is low, and they can synergistically act on the polar interface and the nonpolar interface; the long alkyl chain segment of cardanol provides hydrophobicity, enhances the overall water resistance of the coating, the continuous -CH2- units and cis double bond structure in the carbon chain of cardanol make it have a flexible structure, which is helpful to form a dense crosslinked network and improve the cohesive strength of the coating; the methoxy polyethylene glycol is rich in ether bonds, which can provide hydrophilicity, one end of the methoxy polyethylene glycol is inert methoxy, and the other end is hydroxyl which can react with the epoxy group; compared with the polyethylene glycol with hydroxyl groups at both ends, the methoxy polyethylene glycol can form a more uniform network and stronger hydrolysis resistance with the cardanol-based epoxy resin. At the same time, by adjusting the proportion of hydrophilic and hydrophobic chain segments, the molecular hydrophilicity and hydrophobicity can be balanced to ensure that the ether bonds of the methoxy polyethylene glycol are exposed on the surface layer, so as to optimize the adhesion of the coating to the substrate. In addition, the hydrophobic chain segment maintains the internal structure stability and hydrophobicity of the coating, and the hydrophilic chain segment can migrate to the coating-water interface in seawater to form a hydration layer, which prevents the attachment of fouling organisms through steric hindrance effect, thereby realizing the antifouling function.

[0037] In the compounding system of cardanol-based epoxy resin and methoxy polyethylene glycol, due to the participation of the hydroxyl group at one end of the methoxy polyethylene glycol in the epoxy curing reaction, too high proportion of the methoxy polyethylene glycol may lead to insufficient crosslinking point density, reducing the heat resistance; the unreacted methoxy polyethylene glycol migrates to the surface of the coating, affecting the durability; therefore, the weight ratio of the cardanol-based epoxy resin and the methoxy polyethylene glycol is preferably (4-14): 1, which can ensure that the methoxy polyethylene glycol can both toughen and not destroy the integrity of the cured network.

[0038] In the present application, the adhesion promoter is compounded by silane coupling agent, polydopamine and polycaprolactone. The silane coupling agent forms a dense covalent bonding layer on the metal surface by reaction, and the dopamine spontaneously polymerizes to form a dopamine layer under alkaline conditions. The layer forms non-covalent interactions such as coordination bonds and hydrogen bonds with the metal surface through groups such as pyrocatechol, effectively covering micro defects and enhancing surface wettability; at the same time, the active groups of polydopamine can further react with silane to form a dense and stable composite interface, which can block the penetration of water molecules and corrosive media, and to some extent, improve the corrosion resistance of the coating. At the same time, polycaprolactone introduces a flexible buffer phase into the interface layer through penetration or interface modification. The low rotational barrier of its carbon-carbon single bond makes its molecular chain highly compliant, and its glass transition temperature is much lower than room temperature, so it can be in a high-elastic state at room temperature. It can absorb stress through conformational changes, effectively improving the problem of increased brittleness of the system caused by the compounding of silane coupling agent and polydopamine; when the interface is impacted, the rigid network of silane is responsible for maintaining the stability of the overall structure, the flexible segment of polycaprolactone absorbs energy through deformation, and the dynamic bond of polydopamine prevents the generation and expansion of cracks by its reversible breaking and recombination mechanism, ultimately synergistically improving the toughness and impact resistance of the system.

[0039] In the compounding system of silane coupling agent, polydopamine and polycaprolactone, the silane coupling agent forms a chemical bond with the substrate through a hydrolyzable siloxane group, and its dosage range should ensure sufficient interfacial bonding strength while avoiding the problem of self-condensation caused by excessive dosage; polydopamine realizes broad-spectrum adhesion through catechol groups by virtue of its biomimetic adhesion properties, but the dosage needs to be controlled to prevent brittleness caused by excessive crosslinking; the aliphatic polyester segment of polycaprolactone as a flexible adjusting phase can effectively absorb stress and improve the toughness and impact resistance of the coating; therefore, the weight ratio of silane coupling agent, polydopamine and polycaprolactone is preferably (2-5):(1-3):(2-7), which makes the three components achieve a better synergy in interfacial bonding, adhesion universality and mechanical properties, ensuring the firm combination of the coating with the substrate, and maintaining good flexibility and durability.

[0040] The silane coupling agent is selected from one or more of Z-6026, SICO-A119 and SICO-A210, Z-6026 can provide strong polar amino groups to bond with resin reactive groups, the epoxy groups of SICO-A119 can be copolymerized with various resin systems, and SICO-A210 realizes rapid curing through thiol groups; therefore, all of them contain high-activity siloxane groups, which form stable Si-O-Me bonds with the substrate after hydrolysis, and the flexible chain segments in the molecular structure can relieve interfacial stress. This selection covers three key functional groups of amino, epoxy and mercapto, ensuring wide compatibility with different resin systems and different substrates, while balancing the needs of chemical bonding and interfacial toughening.

[0041] In the present application, the anti-settling agent is compounded by epoxy POSS and polyamide wax. Epoxy POSS is a cubic cage structure composed of siloxane bonds, which is close in size to the molecular chain spacing of polyamide wax and can be physically embedded in the network gap. After the embedding of POSS in the hydrogen-bonded network of polyamide wax, the network density is enhanced through molecular chain entanglement and chemical bonding, reducing the penetration of corrosive media and simultaneously improving the anti-settling and anti-corrosion performance. During the coating scraping and rolling process, the rigid structure of POSS can limit the disordered thermal motion of molecules under the action of shear force, guiding the directional arrangement of polyamide wax, and reconfiguring the traditional hydrogen-bonded network formed by random collision into a high-efficiency self-assembly system centered on POSS, significantly improving the system viscosity, effectively avoiding the delamination and caking caused by the settling of pigments and fillers, and improving the anti-sagging property and the gloss stability of the paint film.

[0042] In the compounded system of epoxy POSS and polyamide wax, if the content of POSS is insufficient, it is difficult to effectively embed in the hydrogen-bonded network of polyamide wax, resulting in insufficient strength of the three-dimensional structure and significant decline in anti-settling performance; if the content of POSS is excessive, the system viscosity will increase dramatically due to excessive crosslinking, affecting the leveling property of the coating during construction; therefore, the weight ratio of epoxy POSS to polyamide wax is preferably 1: (9-12), which covers the transition interval from network-dominated polyamide wax to skeleton-dominated epoxy POSS, balances the anti-settling efficiency and rheological property, and ensures a better solution between storage stability and construction leveling property.

[0043] The epoxy POSS is selected from one or both of Ecotion POSS1010 and Ecotion® POSS101, both of which have a high density of epoxy functional groups on their periphery, can form a stable chemical bonding network with other components in the coating system, significantly improve the anchoring effect and system stability of the anti-settling agent, in addition, the organic-inorganic hybrid structure of Ecotion series POSS makes it have good compatibility with organic resins and polyamide wax, avoiding performance unevenness caused by phase separation.

[0044] In the present application, the wetting dispersant is compounded by oleylamine and polybutyl acrylate. Oleylamine prevents particle agglomeration through electrostatic repulsion, has rapid wetting capacity, and can achieve initial dispersion of pigment particles; polybutyl acrylate maintains long-term dispersion stability through steric hindrance effect, effectively avoids the problem of re-flocculation that may be caused by the use of oleylamine alone, thereby achieving rapid and stable dispersion of pigment particles; in addition, the hydrophobic interaction between the long alkyl chain of oleylamine and polybutyl acrylate can inhibit the surface migration of oleylamine during drying, and the uniform surface tension characteristics of polybutyl acrylate reduce the surface tension gradient of the coating, thereby inhibiting defects such as shrinkage holes and pinholes.

[0045] In the compounded system of oleylamine and polybutyl acrylate, if the oleylamine content is too low, the amine adsorption site is too few, the electrostatic repulsion is weak, and the wetting capacity is reduced; if the oleylamine content is too high, the excess non-polar alkyl chain destroys the steric stabilization effect of polybutyl acrylate, and the polarity imbalance of the system leads to the separation of the resin-solvent-pigment three phases; therefore, the weight ratio of oleylamine and polybutyl acrylate is preferably 1: (4-7), which can ensure higher wetting capacity and stronger stability.

[0046] The epoxy resin A is a bisphenol A type epoxy resin with an epoxy equivalent weight of 200-250 g / mol, and the bisphenol A type epoxy resin is selected from one or both of E-44 and E-51; the defoaming agent is an organosilicon type defoaming agent selected from one or more of BYK-066N, BYK-141, and TEGO Foamex 810; the pigment is selected from one or more of iron red, titanium white powder, and carbon black; the filler is selected from one or more of barium sulfate, mica powder, and talc powder; the first solvent and the second solvent are both selected from one or more of xylene, propylene glycol methyl ether acetate, diacetone alcohol, dimethyl carbonate, and n-butanol; the modified amine curing agent is selected from one or more of EH-226A, Hensamine-4075, and ARADUR 283; and the epoxy promoter is selected from one or both of YH5230 and DMP-30.

[0047] The present application also provides a preparation method of an epoxy connection paint for ships, which comprises the following preparation steps:

[0048] S1: The first solvent, the epoxy resin A, and the epoxy resin B are sequentially added to a dispersing kettle in a predetermined weight ratio, and dispersed for 30-60 minutes;

[0049] S2: The wetting dispersant and the defoaming agent are sequentially added to the dispersing kettle in a predetermined weight ratio, and dispersed for 10-30 minutes;

[0050] S3: The anti-settling agent and the adhesion promoter are sequentially added to the dispersing kettle in a predetermined weight ratio, and dispersed for 10-30 minutes, and then heated to 60-70°C and kept for 30 minutes;

[0051] S4: The pigments and fillers are sequentially added to the dispersion kettle according to the predetermined weight parts, and high-speed dispersion is performed for 30-60 minutes, and then the mixture is transferred to a grinding machine for grinding to a fineness of ≤80 μm;

[0052] S5: The viscosity is adjusted to 90-110 KU using the first solvent, and the mixture is filtered and sealed for storage to obtain the A component;

[0053] S6: The modified amine curing agent, epoxy promoter, and second solvent are sequentially added to the dispersion kettle according to the predetermined weight parts, and stirring is performed until the mixture is uniform, and then dispersion is performed for 15-30 minutes, and the mixture is sealed for storage to obtain the B component;

[0054] S7: The A component and the B component are mixed uniformly according to a weight ratio of (10-15):1 to obtain the epoxy joint paint for ships.

[0055] In step S1, the epoxy resin B is uniformly dispersed by a weight ratio of (4-14):1 of cardanol-based epoxy resin and methoxy polyethylene glycol; in step S2, the wetting dispersant is uniformly dispersed by a weight ratio of 1:(4-7) of oleylamine and polybutyl acrylate; in step S3, the anti-settling agent is uniformly dispersed by a weight ratio of 1:(9-12) of epoxy-based POSS and polyamide wax, and the adhesion promoter is uniformly dispersed by a weight ratio of (2-5):(1-3):(2-7) of silane coupling agent, polydopamine, and polycaprolactone. Example 1

[0056] The present application provides an epoxy joint paint for ships, which comprises an A component and a B component:

[0057] The raw materials of the A component include, by weight fraction, 15 parts of E-44 (epoxy resin A), 8 parts of cardanol-based epoxy resin, 2 parts of methoxy polyethylene glycol, 0.2 parts of Z-6026 (silane coupling agent), 0.1 part of polydopamine, 0.2 parts of polycaprolactone, 0.05 parts of Ecotion POSS1010 (epoxy-based POSS), 0.45 parts of polyamide wax, 0.02 parts of oleylamine, 0.08 parts of polybutyl acrylate, 0.1 parts of BYK-066N (organic silicon-based defoaming agent), 15 parts of iron red (pigment), 25 parts of barium sulfate (filler), and 25 parts of xylene (first solvent).

[0058] The raw materials of the B component include, by weight fraction, 80 parts of EH-226A (modified amine curing agent), 1 part of YH5230 (epoxy promoter), and 5 parts of n-butanol (second solvent).

[0059] The preparation method of the above-mentioned epoxy joint paint for ships comprises the following steps:

[0060] S1: 13 parts of xylene, 15 parts of E-44, and epoxy resin B uniformly pre-dispersed with 8 parts of cardanol-based epoxy resin and 2 parts of methoxy polyethylene glycol were sequentially added into a dispersing kettle, and dispersed for 30 minutes;

[0061] S2: wetting dispersant uniformly pre-dispersed with 0.02 parts of oleylamine and 0.08 parts of polybutyl acrylate, and 0.1 parts of BYK-066N were sequentially added into the dispersing kettle, and dispersed for 10 minutes;

[0062] S3: anti-settling agent uniformly pre-dispersed with 0.05 parts of Ecotion POSS1010 and 0.45 parts of polyamide wax, and adhesion promoter uniformly pre-dispersed with 0.2 parts of Z-6026, 0.1 parts of polydopamine, and 0.2 parts of polycaprolactone were sequentially added into the dispersing kettle, and dispersed for 10 minutes, and then heated to 60°C and kept for 30 minutes;

[0063] S4: 15 parts of iron red and 25 parts of barium sulfate were sequentially added into the dispersing kettle, and high-speed dispersed for 30 minutes, and then transferred to a grinding machine to grind to a fineness of 80 μm;

[0064] S5: 12 parts of xylene were used to adjust the viscosity to 90 KU, and then filtered and sealed to prepare the A component;

[0065] S6: 80 parts of EH-226A, 1 part of YH5230, and 5 parts of n-butanol were sequentially added into a dispersing kettle, uniformly stirred, dispersed for 15 minutes, and then sealed to prepare the B component;

[0066] S7: the A component and the B component were uniformly mixed according to a weight ratio of 10:1 to obtain the epoxy joint paint for ships. Example 2

[0067] The present application provides an epoxy joint paint for ships, which comprises an A component and a B component:

[0068] The raw materials of the A component include, in parts by weight, 30 parts of E-51 (epoxy resin A), 14 parts of cardanol-based epoxy resin, 1 part of methoxy polyethylene glycol, 0.5 parts of SICO-A119 (silane coupling agent), 0.3 parts of polydopamine, 0.7 parts of polycaprolactone, 0.4 parts of Ecotion POSS101 (epoxy-based POSS), 4.6 parts of polyamide wax, 0.2 parts of oleylamine, 1.3 parts of polybutyl acrylate, 0.2 parts of BYK-141 (silicone-based defoaming agent), 20 parts of titanium dioxide (pigment), 30 parts of mica powder (filler), and 40 parts of propylene glycol methyl ether acetate (first solvent).

[0069] The raw materials of the B component include, in parts by weight, 90 parts of Hensamine-4075 (modified amine curing agent), 5 parts of DMP-30 (epoxy promoter), and 10 parts of dimethyl carbonate (second solvent).

[0070] The preparation method of the epoxy connection paint for ships comprises the following steps:

[0071] S1: 20 parts of propylene glycol methyl ether acetate, 30 parts of E-51, and an epoxy resin B uniformly dispersed by 14 parts of cardanol-based epoxy resin and 1 part of methoxy polyethylene glycol are sequentially put into a dispersion kettle, and dispersed for 60 minutes;

[0072] S2: a wetting dispersant uniformly dispersed by 0.2 parts of oleylamine and 1.3 parts of polybutyl acrylate and 0.2 parts of BYK-141 are sequentially put into the dispersion kettle, and dispersed for 30 minutes;

[0073] S3: a sedimentation inhibitor uniformly dispersed by 0.4 parts of Ecotion POSS101 and 4.6 parts of polyamide wax, and an adhesion promoter uniformly dispersed by 0.5 parts of SICO-A119, 0.3 parts of polydopamine and 0.7 parts of polycaprolactone are sequentially put into the dispersion kettle, and dispersed for 30 minutes, and then heated to 70 DEG C and kept for 30 minutes;

[0074] S4: 20 parts of titanium white and 30 parts of mica powder are sequentially put into the dispersion kettle, and dispersed at high speed for 60 minutes, and then ground in a grinder to a fineness of 75 microns;

[0075] S5: 20 parts of propylene glycol methyl ether acetate are used to adjust the viscosity to 110 KU, and then filtered and sealed to obtain the A component;

[0076] S6: 90 parts of Hensamine-4075, 5 parts of DMP-30 and 10 parts of dimethyl carbonate are sequentially put into the dispersion kettle according to the predetermined weight parts, uniformly stirred, dispersed for 30 minutes, and then sealed to obtain the B component;

[0077] S7: the A component and the B component are uniformly mixed according to a weight ratio of 15:1 to obtain the epoxy connection paint for ships. Example 3

[0078] The present application provides an epoxy connection paint for ships, which comprises an A component and a B component:

[0079] The raw materials of the A component include, in parts by weight, 22 parts of E-51 (epoxy resin A), 11 parts of cardanol-based epoxy resin, 1 part of methoxy polyethylene glycol, 0.35 parts of SICO-A210 (silane coupling agent), 0.2 parts of polydopamine, 0.45 parts of polycaprolactone, 0.25 parts of Ecotion® POSS101 (epoxy-based POSS), 2.55 parts of polyamide wax, 0.12 parts of oleylamine, 0.68 parts of polybutyl acrylate, 0.15 parts of TEGO Foamex 810 (silicone-based defoamer), 17 parts of carbon black (pigment), 27 parts of talc (filler), and 32 parts of diacetone alcohol (first solvent).

[0080] The raw materials of the B component include, in parts by weight, 85 parts of ARADUR 283 (modified amine curing agent), 3 parts of DMP-30 (epoxy promoter), and 7 parts of dimethyl carbonate (second solvent).

[0081] The preparation method of the epoxy joint paint for ships described above includes the following steps:

[0082] S1: 16 parts of diacetone alcohol, 22 parts of E-51, and epoxy resin B uniformly dispersed in advance from 11 parts of cardanol-based epoxy resin and 1 part of methoxy polyethylene glycol are sequentially added to a dispersing kettle, and dispersed for 45 minutes;

[0083] S2: wetting dispersant uniformly dispersed in advance from 0.12 parts of oleylamine and 0.68 parts of polybutyl acrylate, and 0.15 parts of TEGO Foamex 810 are sequentially added to the dispersing kettle, and dispersed for 20 minutes;

[0084] S3: anti-settling agent uniformly dispersed in advance from 0.25 parts of Ecotion® POSS101 and 2.55 parts of polyamide wax, and adhesion promoter uniformly dispersed in advance from 0.35 parts of SICO-A210, 0.2 parts of polydopamine, and 0.45 parts of polycaprolactone are sequentially added to the dispersing kettle, and dispersed for 20 minutes, and then heated to 65°C and kept for 30 minutes;

[0085] S4: 17 parts of carbon black and 27 parts of talc are sequentially added to the dispersing kettle, and high-speed dispersed for 45 minutes, and then transferred to a grinding machine to be ground to a fineness of 70 μm;

[0086] S5: 16 parts of diacetone alcohol are used to adjust the viscosity to 100 KU, and the A component is obtained after filtration and sealed storage;

[0087] S6: 85 parts of ARADUR 283, 3 parts of DMP-30, and 7 parts of dimethyl carbonate are sequentially added to the dispersing kettle according to the predetermined parts by weight, and stirred uniformly, dispersed for 22 minutes, and then sealed and stored to obtain the B component;

[0088] S7: The A component and the B component are mixed uniformly according to a weight ratio of 12:1 to obtain the epoxy joint paint for ships.

[0089] Comparative Example 1

[0090] The present comparative example provides an epoxy joint paint for ships, which is different from Example 1 in that the present comparative example replaces the methoxypolyethylene glycol with an equal amount of cardanol-based epoxy resin.

[0091] Comparative Example 2

[0092] The present comparative example provides an epoxy joint paint for ships, which is different from Example 1 in that the present comparative example replaces the polydopamine with an equal amount of Z-6026.

[0093] Comparative Example 3

[0094] The present comparative example provides an epoxy joint paint for ships, which is different from Example 1 in that the present comparative example replaces the polycaprolactone with an equal amount of Z-6026.

[0095] Comparative Example 4

[0096] The present comparative example provides an epoxy joint paint for ships, which is different from Example 1 in that the present comparative example replaces the Ecotion POSS1010 with an equal amount of polyamide wax.

[0097] Comparative Example 5

[0098] The present comparative example provides an epoxy joint paint for ships, which is different from Example 1 in that the present comparative example replaces the polybutyl acrylate with an equal amount of oleylamine.

[0099] The present application respectively prepares a 100±20 μm thick coating film of the paint of Examples 1-3 and Comparative Examples 1-5 on a steel substrate, and performs performance detection, and the detection results are shown in Table 1.

[0100] Table 1: Performance detection method of paint film and performance detection results of epoxy joint paint for ships

[0101]

[0102] As shown in Table 1, the present application provides an epoxy paint with high adhesion, strong corrosion resistance, strong antifouling property and long-term stability, which is suitable for joint paint for ships.

[0103] By comparing Comparative Example 1 and Example 1, it is found that the addition of methoxypolyethylene glycol in the epoxy joint paint for ships enhances the cathodic disbonding resistance, shallow sea immersion property, and passes the dynamic simulation test.

[0104] Comparative Example 2 and Example 1, it was found that the addition of polydopamine to the epoxy tiecoat for ships enhanced adhesion, flexibility, impact resistance, cathodic disbondment resistance, shallow sea immersion, and passed the dynamic simulation test.

[0105] Comparative Example 3 and Example 1, it was found that the addition of polycaprolactone to the epoxy tiecoat for ships enhanced adhesion, flexibility, impact resistance, cathodic disbondment resistance, shallow sea immersion, and passed the dynamic simulation test.

[0106] Comparative Example 4 and Example 1, it was found that the addition of epoxy-based POSS to the epoxy tiecoat for ships reduced volatile organic content, enhanced gloss stability, viscosity, sag resistance, cathodic disbondment resistance, shallow sea immersion, and passed the dynamic simulation test.

[0107] Comparative Example 5 and Example 1, it was found that the addition of polybutyl acrylate to the epoxy tiecoat for ships reduced volatile organic content, enhanced gloss stability, and shallow sea immersion.

[0108] Obviously, the above examples are merely illustrative and not intended to limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. Here, it is not necessary and impossible to exhaust all embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. An epoxy bonding paint for ships, characterized in that, Includes component A and component B; Component A, by weight, comprises the following raw materials: 15-30 parts epoxy resin A, 10-15 parts epoxy resin B, 0.1-1.5 parts wetting and dispersing agent, 0.5-5 parts anti-settling agent, 0.1-0.2 parts defoamer, 15-20 parts pigment, 25-30 parts filler, 0.5-1.5 parts adhesion promoter, and 25-40 parts first solvent; The epoxy resin A is a bisphenol A type epoxy resin with an epoxy equivalent of 200-250 g / mol. The epoxy resin B is a compound of cashew phenol-based epoxy resin and methoxy polyethylene glycol. The adhesion promoter is a compound of silane coupling agent, polydopamine and polycaprolactone; The anti-settling agent is a compound of epoxy POSS and polyamide wax; The wetting and dispersing agent is a compound of oleylamine and polybutyl acrylate; The B component, by weight, comprises the following raw materials: 80-90 parts of modified amine curing agent, 1-5 parts of epoxy accelerator, and 5-10 parts of second solvent; The components A and B are mixed at a weight ratio of (10-15):

1.

2. The epoxy bonding paint for ships according to claim 1, characterized in that: The weight ratio of the cashew phenol-based epoxy resin to the methoxy polyethylene glycol is (4-14):

1.

3. The epoxy bonding paint for ships according to claim 1, characterized in that: The weight ratio of the silane coupling agent, polydopamine, and polycaprolactone is (2-5):(1-3):(2-7). The silane coupling agent is selected from one or more of Z-6026, SICO-A119 and SICO-A210.

4. The epoxy bonding paint for ships according to claim 1, characterized in that: The weight ratio of the epoxy-based POSS to the polyamide wax is 1:(9-12). The epoxy group POSS is selected from one or both of Ecotion POSS1010 and Ecotion® POSS101.

5. The epoxy bonding paint for ships according to claim 1, characterized in that: The weight ratio of oleylamine to polybutyl acrylate is 1:(4-7).

6. The epoxy bonding paint for ships according to claim 1, characterized in that: The bisphenol A type epoxy resin is selected from one or both of E-44 and E-51; The defoamer is a silicone-based defoamer, and the silicone-based defoamer is selected from one or more of BYK-066N, BYK-141, and TEGOFoamex 810; The pigment is selected from one or more of iron oxide red, titanium dioxide, and carbon black; The filler is selected from one or more of barium sulfate, mica powder, and talc powder; The first solvent and the second solvent are both selected from one or more of xylene, propylene glycol methyl ether acetate, diacetone alcohol, dimethyl carbonate, and n-butanol; The modified amine curing agent is selected from one or more of EH-226A, Hensamine-4075, and ARADUR 283; The epoxy accelerator is selected from one or both of YH5230 and DMP-30.

7. The method for preparing the epoxy bonding paint for ships according to any one of claims 1-6, characterized in that: Includes the following steps: S1: Add the first solvent, epoxy resin A and epoxy resin B into the dispersion vessel in the predetermined weight parts and disperse for 30-60 minutes. S2: Add the wetting and dispersing agent and the defoamer into the dispersion vessel in the predetermined weight parts and disperse for 10-30 minutes; S3: Add the anti-settling agent and adhesion promoter to the dispersion vessel in the predetermined weight proportions, disperse for 10-30 minutes, heat to 60-70℃, and keep warm for 30 minutes; S4: Add the pigments and fillers into the dispersion vessel in the predetermined weight proportions, disperse at high speed for 30-60 minutes, and then grind them in a grinder until the fineness is ≤80μm; S5: Adjust the viscosity to 90-110 KU using the first solvent, filter, seal and store to obtain component A; S6: Add the modified amine curing agent, epoxy accelerator, and second solvent into the dispersion vessel in the predetermined weight parts, stir evenly, disperse for 15-30 minutes, and seal and store to obtain component B; S7: The A component and the B component are mixed evenly at a weight ratio of (10-15):1 to obtain the epoxy bonding paint.

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