Water-based resin, water-based coating material, and corrosion-resistant coating layer

Abstract

We provide a water-based resin. [Solution] The aqueous resin is an ammonium salt formed by reacting an aromatic acid with an alkaline compound neutralization ring-opening intermediate compound. The alkaline compound neutralization ring-opening intermediate compound is formed by neutralizing the ring-opening intermediate compound with an alkaline compound, and the ring-opening intermediate compound is formed by carrying out a ring-opening reaction of a copolymer containing maleic anhydride using a tertiary amino alcohol. The chemical structures of the copolymer containing maleic anhydride, the tertiary amino alcohol, and the aromatic acid are as follows (wherein the formulas, the symbols are as defined in the specification). TIFF2026092659000036.tif25129

Description

[Technical Field]

[0001] This technical field relates to aqueous resins. [Background technology]

[0002] Currently, the main anticorrosion coating materials for metal plates and screws on the market are solvent-based, which do not meet the international trend towards carbon reduction. Water-based anticorrosion coating materials are gradually gaining attention, but their performance is not sufficiently good. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 10669441 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The poor performance of water-based anticorrosive coating materials is a result of the hydrophilicity of the water-based resins in these coatings. The hydrophilicity of the water-based resins affects the corrosion resistance of the films formed from the coating materials. If the hydrophilicity of the water-based resins is too low, it affects the compatibility and stability of the coating material formulation. If the hydrophilicity of the water-based resins is too high, it affects the corrosion resistance of the film. [Means for solving the problem]

[0005] One embodiment of the present disclosure provides an aqueous resin which is an ammonium salt formed by reacting an aromatic acid with an alkaline compound neutralization ring-opening intermediate compound. The alkaline compound neutralization ring-opening intermediate compound is formed by neutralizing a ring-opening intermediate compound with an alkaline compound, and the ring-opening intermediate compound is formed by a ring-opening reaction of a maleic anhydride copolymer with a tertiary amino alcohol. The maleic anhydride copolymer is TIFF2026092659000001.tif3362 has a chemical structure, where R 1 is H or CH3, R 2 is H, CH3, or C6H5, m:n = 1:3 to 3:1, and n = 4 to 20. The tertiary amino alcohol is TIFF2026092659000002.tif2738 has a chemical structure, where R 3 is a C 1-10 alkylene group, R 4 is H, a C 1-10 alkyl group, or a C 6-12 aromatic group, and 5 and R 6 each is independently a C 1-10 alkyl group or a C 6-12 aromatic group. The aromatic acid is TIFF2026092659000003.tif3466 has a chemical structure, where R 7 is H, a C 1-10 alkyl group, or a C 6-12 aromatic group, R 8 is a C 1-5 alkylene group or TIFF2026092659000004.tif1332.

[0006] One embodiment of the present disclosure provides an aqueous coating material comprising 100 parts by weight of water and 50 to 100 parts by weight of the described aqueous resin.

[0007] One embodiment of the present disclosure provides a corrosion - resistant coating layer covering the surface of a metal article, where the corrosion - resistant coating layer contains the described aqueous resin.

Advantages of the Invention

[0008] The aqueous resin having high corrosion resistance can enhance the performance of the aqueous corrosion - resistant coating material and expand the application fields of the aqueous corrosion - resistant coating material.

[0009] In the following embodiments, a detailed description will be given.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details.

[0011] One embodiment of the present disclosure provides an aqueous resin that is an ammonium salt formed by reacting an aromatic acid with an alkaline compound-neutralized ring-opening intermediate compound. The alkaline compound-neutralized ring-opening intermediate compound is formed by neutralizing a ring-opening intermediate compound with an alkaline compound, and the ring-opening intermediate compound is formed by performing a ring-opening reaction of a copolymer containing maleic anhydride with a tertiary amino alcohol. The copolymer containing maleic anhydride can have the chemical structure of TIFF2026092659000005.tif3363, where R is H or CH3, R 1 is H, CH3, or C6H5, m:n = 1:3 to 3:1, and n = 4 to 20. Note that the copolymer is a random copolymer, not a block copolymer. The tertiary amino alcohol can have the chemical structure of TIFF2026092659000006.tif2841, where R 2 is a C alkylene group, R 3 is C 1-10 is an alkyl group, R 4 is H, C 1-10 is an alkyl group, or C 6-12 is an aromatic group, and each of R 5 and R 6 is independently a C 1-10 alkyl group or C 6-12 aromatic group. The aromatic acid can have the chemical structure of TIFF2026092659000007.tif3366, where R is H, C 7 is an alkyl group, or C 1-10 is an aromatic group, R 6-12 is C 8 is C1-5 Alkylene group or The filename is TIFF2026092659000008.tif1232.

[0012] In one embodiment of the present disclosure, a copolymer containing maleic anhydride first reacts with a tertiary amino alcohol; that is, the maleic anhydride in the copolymer and the hydroxyl group of the tertiary amino alcohol undergo a ring-opening reaction to obtain a ring-opening intermediate compound. For example, the reaction is shown below. [ka] In the above equation, o + p = n and p > 0. o depends on the molar ratio of maleic anhydride repeating units to tertiary amino alcohol. Theoretically, ring opening should be complete (o = 0) when the molar ratio of maleic anhydride repeating units to tertiary amino alcohol is 1 or less, but in reality, a small amount of maleic anhydride may remain unopened (o is approximately 0). Simply put, o can be 0 or greater.

[0013] The aqueous resins of this disclosure can be used in coating materials. In some embodiments, the aqueous resins of this disclosure are proposed to be used as contents of a corrosion-resistant coating layer. The repeating maleic anhydride units of the copolymer and the tertiary amino alcohol can have a molar ratio of 1:1.2 to 1:0.8. If the amount of tertiary amino alcohol is too high, there will be too much free (unreacted) tertiary amino alcohol, which may affect the efficient amount of ammonium salt subsequently formed and reduce the corrosion resistance of the coating layer. If the amount of tertiary amino alcohol is too low, the amount of ammonium salt subsequently formed will be insufficient and reduce the corrosion resistance of the coating layer.

[0014] Subsequently, the ring-opening intermediate compound was neutralized by mixing it with an alkaline compound (e.g., ammonia, triethanolamine, or another alkaline solution) and an appropriate amount of water to obtain the alkaline compound neutralization ring-opening intermediate compound. When the alkaline compound is ammonia, the reaction is shown below. [ka] In the above reaction, ammonia can neutralize the carboxylic acid from the ring-opening reaction of the tertiary amino alcohol and maleic anhydride, and further, it can undergo a ring-opening reaction with the small amount of unopened maleic anhydride (if present), and neutralize the carboxylic acid from the ring-opening reaction of ammonia and maleic anhydride. Theoretically, the number of moles of ammonia should be the sum of twice the number of moles of unopened maleic anhydride and the number of moles of opened maleic anhydride (i.e., 20+p).

[0015] Subsequently, the neutralization ring-opening intermediate compound and the aromatic acid were heated to 40°C to 50°C to react so that the carboxylic acid group of the aromatic acid and the tertiary amine group of the neutralization ring-opening intermediate compound would form an ammonium salt, thereby obtaining an aqueous solution of the aqueous resin. The reaction is shown below. [ka] In some embodiments, when the aqueous resin of the present disclosure is proposed to be used as a component of a corrosion-resistant coating layer, the aromatic acid and tertiary amino alcohol may have a molar ratio of 1.2:1 to 1:1. If the amount of aromatic acid is too high or too low, the corrosion resistance of the coating layer formed from the aqueous resin will be reduced.

[0016] It should be noted that if the neutralization ring-opening intermediate compound and the aromatic acid are simply mixed without being heated and reacted, an ammonium salt cannot be formed. When the above mixture is used as the content of a corrosion-preventive coating layer, the corrosion resistance of the coating layer will be poor (see Comparative Example 6 in this disclosure).

[0017] On the other hand, when a ring-opening reaction is carried out using a primary amine compound (e.g., ethylenediamine), the primary amine and aromatic acid of the neutralization ring-opening intermediate compound undergo an acylation reaction other than the formation of an ammonium salt (see Comparative Example 3 in this disclosure). Therefore, when the aqueous resin formed from the above reaction is used as the content of a corrosion-resistant coating layer, the corrosion resistance of the coating layer becomes poor.

[0018] In some embodiments, the copolymer containing maleic anhydride is It has the chemical structure of TIFF2026092659000012.tif4271. This copolymer is called styrene-maleic anhydride copolymer (SMA).

[0019] In some embodiments, tertiary amino alcohols are It has the chemical structure of TIFF2026092659000013.tif2537.

[0020] In some embodiments, aromatic acids are It has the chemical structure of TIFF2026092659000014.tif3878. This aromatic acid is coumaric acid (R 7 (where H is), or coumaric acid derivative (R 7 However, C 1-10 Alkyl or C 6-12 It is called an aromatic group.

[0021] In some embodiments, when preparing an aqueous coating material for a corrosion-resistant coating layer using an aqueous resin, the aqueous resin has a weight-average molecular weight (Mw) of 1500 g / mol to 5000 g / mol. If the Mw of the aqueous resin is too high, the solubility of the aqueous resin decreases, reducing the effective contents that dissolve in water and lowering the corrosion resistance of the coating layer. If the Mw of the aqueous resin is too low, the film moldability of the coating layer decreases, and the corrosion resistance of the coating layer also decreases.

[0022] One embodiment of the present disclosure provides an aqueous coating material comprising 100 parts by weight of water and 50 to 100 parts by weight of the aqueous resin described. If the amount of aqueous resin is too high, the aqueous resin will precipitate and become unusable. If the amount of aqueous resin is too low, the film moldability of the coating layer will be insufficient and the corrosion resistance of the coating layer will be reduced.

[0023] In some embodiments, the aqueous coating material may further contain 0.1 to 3 parts by weight of additives, which may be leveling agents, defoaming agents, preservatives, or a combination thereof. Additives are beneficial in improving the processability and storage capacity of the coating material.

[0024] In some embodiments, when an aqueous coating material is used to form a corrosion-resistant coating layer, the corrosion-resistant coating layer may further contain 10 to 100 parts by weight of sol-gel, where the sol-gel contains a silane compound, a metal salt, and water. The sol-gel can further improve the corrosion resistance of the coating layer. For methods of forming the sol-gel and specific compositions, refer to Taiwan Patent No. I764461.

[0025] In one embodiment of this disclosure, an aqueous coating material can be used on a metal article. The aqueous coating material is coated onto the surface of the metal article and then dried to form a corrosion-resistant coating layer covering the surface of the metal article, wherein the corrosion-resistant coating layer includes an aqueous resin. In some embodiments, the corrosion-resistant coating layer may further include the additives and sol gels described. As is known from experiments, aqueous resins can efficiently improve the corrosion resistance of the corrosion-resistant coating layer. The metal article may be, but is not limited to, a screw, an aluminum plate, or an iron plate.

[0026] Hereinafter, exemplary embodiments will be described in detail so as will be readily apparent to those skilled in the art. The concept of the present invention can be embodied in various forms, without being limited to the exemplary embodiments described herein. [Examples]

[0027] Example 1 500 g of styrene-maleic anhydride copolymer (SMA, commercially available SMA1000 from Cray Valley), 178 g of dimethylethanolamine (DMAE, 2 mol), 3.5 g of the acid catalyst p-toluenesulfonic acid (PTSA, 0.02 mol), and 400 mL of the solvent methyl ethyl ketone were added to a reaction vessel. The mixture was then heated to 80°C to 100°C and stirred, reacting for 6 to 8 hours. After cooling, the mixture was filtered and purified to obtain the ring-opening intermediate compound. The reaction is shown below. [ka] In the above equation, m=8, n=8, o+p=8, and o is approximately 0 (a small amount did not open the ring).

[0028] The ring-opening intermediate compound, ammonia, and an appropriate amount of water were added to the reaction vessel, and then the mixture was heated to 40°C to 50°C and stirred for 2 to 3 hours to obtain the ammonia-neutralized ring-opening intermediate compound. The reaction is shown below. [ka] In the above reaction, ammonia was able to neutralize the carboxylic acid group from the ring-opening reaction between DMAE and maleic anhydride, and furthermore, it was able to undergo a ring-opening reaction with a small amount of unopened maleic anhydride, thereby neutralizing the carboxylic acid group from the ring-opening reaction between ammonia and maleic anhydride.

[0029] Subsequently, 164 g (1 mole) of coumaric acid was added to a reaction vessel containing the ammonia neutralization ring-opening intermediate compound, and the mixture was stirred at 40°C to 50°C for 1 to 2 hours. The carboxylic acid group of coumaric acid and the tertiary amine group of the ammonia neutralization ring-opening intermediate compound formed an ammonium salt, thereby yielding an aqueous solution of the aqueous resin. The aqueous resin had a weight-average molecular weight of 2400 g / mol. The reaction is shown below. [ka]

[0030] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 600 hours in a salt spray test.

[0031] Example 2 The reaction in Example 2 was repeated from Example 1, with the only difference being that 248 g (1 mole) of the coumaric acid derivative was added to a reaction vessel containing an ammonia-neutralized ring-opening intermediate compound, and then stirred at 40°C to 50°C for 1 to 2 hours. The carboxylic acid group of the coumaric acid derivative and the tertiary amine group of the ammonia-neutralized ring-opening intermediate compound formed an ammonium salt, thereby yielding an aqueous solution of the aqueous resin. The aqueous resin had a weight-average molecular weight of 2500 g / mol. The reaction is shown below. [ka] In the above formula, R 7 It is a hexyl group.

[0032] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 800 hours in a salt spray test.

[0033] Example 3 The reaction in Example 3 was a repetition of Example 1, with the only difference being that 254 g (1 mole) of the coumaric acid derivative was added to a reaction vessel containing an ammonia-neutralized ring-opening intermediate compound, and then stirred at 40°C to 50°C for 1 to 2 hours. The carboxylic acid group of the coumaric acid derivative and the tertiary amine group of the ammonia-neutralized ring-opening intermediate compound formed an ammonium salt, thereby yielding an aqueous solution of the aqueous resin. The aqueous resin had a weight-average molecular weight of 2500 g / mol. The reaction is shown below. [ka] In the above formula, R 7 It is a phenyl group.

[0034] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 800 hours in a salt spray test.

[0035] Example 4 500 g of styrene-maleic anhydride copolymer (SMA, commercially available SMA1000F from Cray Valley), 178 g of DMAE (2 mol), 3.5 g of PTSA (0.02 mol), and 400 mL of methyl ethyl ketone (the solvent) were added to a reaction vessel. The mixture was then heated to 80°C to 100°C, stirred, and reacted for 6 to 8 hours. After cooling, the mixture was filtered and purified to obtain the ring-opening intermediate compound. The reaction is shown below. [ka] In the above equation, m=16, n=16, and o+p=16, where o is approximately 0 (a small amount did not open the ring).

[0036] The ring-opening intermediate compound, ammonia, and an appropriate amount of water were added to the reaction vessel, and then the mixture was heated to 40°C to 50°C and stirred for 2 to 3 hours to obtain the ammonia-neutralized ring-opening intermediate compound. The reaction is shown below. [ka] In the above reaction, ammonia was able to neutralize the carboxylic acid group from the ring-opening reaction between DMAE and maleic anhydride, and furthermore, it was able to undergo a ring-opening reaction with a small amount of unopened maleic anhydride, thereby neutralizing the carboxylic acid group from the ring-opening reaction between ammonia and maleic anhydride.

[0037] Subsequently, 164 g (1 mole) of coumaric acid was added to a reaction vessel containing the ammonia neutralization ring-opening intermediate compound, and the reaction was stirred at 40°C to 50°C for 1 to 2 hours. The carboxylic acid group of coumaric acid and the tertiary amine group of the ammonia neutralization ring-opening intermediate compound formed an ammonium salt, thereby yielding an aqueous solution of the aqueous resin. The aqueous resin had a weight-average molecular weight of 4500 g / mol. The reaction is shown below. [ka]

[0038] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 600 hours in a salt spray test.

[0039] Example 5 750 g of styrene-maleic anhydride copolymer (SMA, commercially available SMA2000 from Cray Valley), 178 g of DMAE (2 mol), 3.5 g of PTSA (0.02 mol), and 400 mL of methyl ethyl ketone (the solvent) were added to a reaction vessel. The mixture was then heated to 80°C to 100°C, stirred, and reacted for 6 to 8 hours. After cooling, the mixture was filtered and purified to obtain the ring-opening intermediate compound. The reaction is shown below. [ka] In the above equation, m=16, n=8, o+p=8, and o is approximately 0 (a small amount did not open the ring).

[0040] The ring-opening intermediate compound, ammonia, and an appropriate amount of water were added to the reaction vessel, and then the mixture was heated to 40°C to 50°C and stirred for 2 to 3 hours to obtain the ammonia-neutralized ring-opening intermediate compound. The reaction is shown below. [ka] In the above reaction, ammonia was able to neutralize the carboxylic acid group from the ring-opening reaction between DMAE and maleic anhydride, and furthermore, it was able to undergo a ring-opening reaction with a small amount of unopened maleic anhydride, thereby neutralizing the carboxylic acid group from the ring-opening reaction between ammonia and maleic anhydride.

[0041] Subsequently, 164 g (1 mole) of coumaric acid was added to a reaction vessel containing the ammonia neutralization ring-opening intermediate compound, and the mixture was stirred at 40°C to 50°C for 1 to 2 hours. The carboxylic acid group of coumaric acid and the tertiary amine group of the ammonia neutralization ring-opening intermediate compound formed an ammonium salt, thereby yielding an aqueous solution of the aqueous resin. The aqueous resin had a weight-average molecular weight of 3400 g / mol. The reaction is shown below. [ka]

[0042] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 600 hours in a salt spray test.

[0043] Comparative Example 1 A mixture of 100g of SMA (SMA1000, commercially available from Cray Valley), 100g of water, 0.2g of leveling agent (BYK333, commercially available from BYK), 0.1g of defoaming agent (BYK021, commercially available from BYK), and 0.01g of preservative (Kathon CG, commercially available from Rohm and Haas) was mixed, but it could not be made compatible and failed to function as a water-based coating material.

[0044] Comparative Example 2 Water was added to the ammonia neutralization ring-opening intermediate compound of Example 1 to form an aqueous solution, in which the ammonia neutralization ring-opening intermediate compound and water had a weight ratio of 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of an aqueous solution of the ammonia neutralization ring-opening intermediate compound to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. Next, the screws were subjected to a salt spray test in accordance with the ASTM B117 standard. The screws corroded approximately 200 hours after the salt spray test.

[0045] Comparative Example 3 500 g of SMA (SMA1000, commercially available from Cray Valley), 60 g of ethylenediamine (1 mol), 3.5 g of PTSA (0.02 mol), and 400 mL of methyl ethyl ketone (the solvent) were added to a reaction vessel. The mixture was then stirred at room temperature and reacted for 12 hours. The mixture was then filtered and purified to obtain the ring-opening intermediate compound. The reaction is shown below. [ka] In the above equation, m=8, n=8, o+p=8, and o is approximately 0 (a small amount did not open the ring).

[0046] 560 g of the ring-opening intermediate compound, 164 g of coumaric acid (1 mole), and 3.1 g of the catalyst N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) were mixed and stirred at room temperature for 24 hours. The primary amine group of the ring-opening intermediate compound reacted with the carboxylic acid group of coumaric acid to form an amide, thereby obtaining an aqueous solution of the aqueous resin. The reaction is shown below. [ka]

[0047] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 400 hours in a salt spray test.

[0048] Comparative Example 4 A polyester (Gardbond®, commercially available from BASF) supplied as an aqueous resin was dissolved in water. In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous resin solution and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. Next, the screws were subjected to a salt spray test in accordance with the ASTM B117 standard. The screws corroded approximately 100 hours after the salt spray test.

[0049] Comparative Example 5 Stainless steel screws (Series 4) were selected and subjected to a salt spray test according to the ASTM B117 standard. The screws corroded in less than 72 hours during the salt spray test.

[0050] Example 6 50 g of a corrosion inhibitor, such as a sol-gel (containing a compound, metal salt, and water; see Example 1 of Taiwan Patent No. I764461), was added to the aqueous coating material of Example 2. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form a corrosion-resistant coating layer on the screws. The screws were then subjected to a salt spray test according to ASTM B117 standard. The screws corroded after 1000 hours in the salt spray test.

[0051] Comparative Example 6 The procedure in Example 1 was repeated, with the only difference in Comparative Example 6 being that 164 g (1 mole) of coumaric acid was added to a reaction vessel containing the ammonia neutralization ring-opening intermediate compound, and then mixed (instead of reacting the carboxylic acid group of coumaric acid with the tertiary amine group of the ammonia neutralization ring-opening intermediate compound to form an ammonium salt), thereby obtaining an aqueous solution of the aqueous resin (for example, a mixture of the ammonia neutralization ring-opening intermediate compound and coumaric acid).

[0052] In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), and 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas) were added to 100 g of the aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded after approximately 300 hours in a salt spray test.

[0053] Comparative Example 7 A polyester (Gardbond®, commercially available from BASF) supplied as an aqueous resin was dissolved in water. In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas), and 5 g of coumaric acid were added to 100 g of an aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form an anticorrosion coating layer on the screws. Next, the screws were subjected to a salt spray test in accordance with the ASTM B117 standard. The screws corroded approximately 300 hours after the salt spray test.

[0054] Comparative Example 8 A polyester (Gardbond®, commercially available from BASF) supplied as an aqueous resin was dissolved in water. In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas), and 50 g of a sol gel (containing a compound, a metal salt, and water; see Example 1 of Taiwan Patent No. I764461) were added to 100 g of an aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form a corrosion-resistant coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded approximately 200 hours after the salt spray test.

[0055] Comparative Example 9 A polyester (Gardbond®, commercially available from BASF) supplied as an aqueous resin was dissolved in water. In the aqueous solution of the aqueous resin, the weight ratio of the aqueous resin to water was approximately 100:100. Additives such as 0.2 g of a leveling agent (BYK333, commercially available from BYK), 0.1 g of an antifoaming agent (BYK021, commercially available from BYK), 0.01 g of a preservative (Kathon CG, commercially available from Rohm and Haas), 5 g of coumaric acid, and 50 g of a sol gel (containing a compound, a metal salt, and water; see Example 1 of Taiwan Patent No. I764461) were added to 100 g of an aqueous solution of the aqueous resin and mixed to obtain an aqueous coating material. The contents of the aqueous coating material were miscible without suspension or precipitation. The prepared aqueous coating material was coated onto stainless steel screws (Series 4) to form a film with a thickness of 6 to 10 micrometers. The film was baked at 200°C for 10 minutes to form a corrosion-resistant coating layer on the screws. The screws were then subjected to a salt spray test according to the ASTM B117 standard. The screws corroded approximately 400 hours after the salt spray test.

[0056] It will be apparent to those skilled in the art that various modifications and variations can be applied to the disclosed methods and materials. The specification and examples are to be considered merely illustrative, and the true scope of this disclosure is intended to be shown by the following claims and their equivalents.

Claims

1. An aqueous resin which is an ammonium salt formed by reacting an aromatic acid with an alkaline compound neutralization ring-opening intermediate compound, The aforementioned alkaline compound neutralization ring-opening intermediate compound is formed by neutralizing the ring-opening intermediate compound with an alkaline compound. The aforementioned ring-opening intermediate compound is formed by a ring-opening reaction of a copolymer containing maleic anhydride with a tertiary amino alcohol. The copolymer containing maleic anhydride is It has the chemical structure of, in the formula, R 1 is H or CH 3 And R 2 H, CH 3 , or C 6 H 5 And m:n = 1:3 to 3:1, and n = 4 to 20, The aforementioned tertiary amino alcohol is having the chemical structure, wherein R 3 is a C 1-10 alkylene group, and R 4 is H, a C 1-10 alkyl group, or a C 6-12 aromatic group, and, each of R 5 and R 6 is independently a C 1-10 alkyl group or a C 6-12 aromatic group, The aforementioned aromatic acid is It has the chemical structure of, in the formula, R 7 H, C 1-10 Alkyl alkyl group, or C 6-12 It is an aromatic group, R 8 is C 1-5 Alkylene group or It is a water-based resin.

2. The copolymer containing maleic anhydride is The aqueous resin according to claim 1, having the chemical structure.

3. The aforementioned tertiary amino alcohol is The aqueous resin according to claim 1, having the chemical structure.

4. The aforementioned aromatic acid is The aqueous resin according to claim 1, having the chemical structure.

5. The aqueous resin according to claim 1, wherein the aqueous resin has a weight-average molecular weight of 1500 to 5000 g / mol.

6. The aqueous resin is The aqueous resin according to claim 1, having the chemical structure of the formula, wherein o + p = n, p > 0, and o is 0 or greater.

7. 100 parts by weight of water and 50 to 100 parts by weight of the aqueous resin according to claim 1, A water-based coating material containing [a specific component].

8. The aqueous coating material according to claim 7, further comprising 0.1 to 3 parts by weight of an additive, wherein the additive is a leveling agent, an antifoaming agent, a preservative, or a combination thereof.

9. The aqueous coating material according to claim 7, further comprising 10 to 100 parts by weight of a sol gel, wherein the sol gel comprises a silane compound, a metal salt, and water.

10. A corrosion-resistant coating layer covering the surface of a metal article, wherein the corrosion-resistant coating layer contains the aqueous resin described in claim 1.

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