Corrosion-resistant environment-friendly ink and preparation method thereof

Abstract

The present application relates to a kind of corrosion-resistant environment-friendly ink and its preparation method, belong to water-based ink technical field.The components of the ink are: water-based pigment 8-12wt%, colorant 1.7-2.2wt%, defoaming agent 0.3-0.4wt%, leveling agent 0.25-0.3wt%, light stabilizer 0.1-0.12wt% and thickening agent 1.2-1.5wt%, the rest is modified acrylic ester emulsion;Modified acrylic ester emulsion as connecting material, it constructs the bifunctional structure of " hydrophilic quaternary ammonium interface-hydrophobic fluorine alkyl core " in molecular chain, provide hydrophilic dispersibility by quaternary ammonium structure, during ink drying process, water is separated from hydrophilic quaternary ammonium interface, fluorine structure of low surface energy migrates to the interface of high surface energy droplet spread, closes hydrophilic passage, while weakening the electrostatic repulsion between interface, improve ink layer compactness, effectively resist external medium erosion.

Description

Technical Field

[0001] The present invention belongs to the technical field of water-based inks, and in particular relates to a corrosion-resistant and environmentally friendly ink and a preparation method thereof. Background Art

[0002] With increasingly stringent global environmental regulations and the growing popularity of sustainable development, the printing industry is undergoing a major shift toward environmentally friendly materials. Water-based inks, which use water as their primary dispersion medium or diluent, significantly reduce volatile organic compound emissions, fundamentally addressing the environmental pollution and occupational health hazards associated with solvent-based inks. They are widely recognized as the most promising environmentally friendly ink technology and represent a key future development trend in the ink industry.

[0003] The key to achieving stable dispersion in water-based inks lies in their waterborne binders. These binders are typically composed of specially modified resins, achieving water-based properties by introducing strong hydrophilic groups (such as hydroxyl, carboxyl, and sulfonic acid groups) into their molecular structures. Among these, waterborne acrylic resins are among the most widely used waterborne binders due to their excellent film-forming properties, gloss, adhesion, weather resistance, and relative ease of molecular design. In aqueous systems, these hydrophilic groups spontaneously migrate to the interface between the resin particles and water, effectively encapsulating the hydrophobic polymer chains within, forming tiny droplets characterized by a hydrophobic core and a hydrophilic shell. This structure enables the originally water-insoluble hydrophobic resin to be evenly and stably dispersed in water, forming an emulsion or dispersion.

[0004] However, despite the significant environmental advantages of water-based inks, their performance is often inferior to that of traditional solvent-based inks in practical applications, especially in areas requiring good corrosion resistance (such as outdoor signs and packaging materials). The fundamental reason for this performance gap lies in the essential differences in the drying and film-forming mechanisms of the two:

[0005] Solvent-based inks dry and form films: During the drying process, the organic solvent, which serves as the dispersion medium, gradually evaporates and precipitates from the spaces between the macromolecular polymer chains. As the solvent is removed, the polymer chains are free to move and align, ultimately spreading evenly and continuously to form a dense, gapless ink film. This dense structure effectively blocks the penetration and erosion of corrosive media.

[0006] Water-based ink drying and film formation: The drying of water-based ink is a process of water evaporation. Water is primarily present in the aqueous phase between the droplets and in the hydrophilic layer on the droplet surface. As water evaporates, especially after precipitation from the hydrophilic interface between the droplets, the movement of the polymer segments "anchored" by the hydrophilic groups at the interface becomes restricted. These segments struggle to achieve the full spreading and fusion that polymers in solvent-based systems achieve. Ultimately, in the cured ink layer, the original hydrophilic group-rich regions fail to fully close, leaving behind a large number of interconnected microscopic "hydrophilic channels."

[0007] These residual hydrophilic channels constitute weak links and penetration pathways within the ink layer. External corrosive media (such as water, acids, alkalis, and salt ions) can easily penetrate the ink layer through these hydrophilic channels, even reaching the substrate surface. This can cause swelling, hydrolysis, discoloration, and flaking of the ink layer, or accelerate corrosion of the substrate itself, ultimately leading to functional failure and cosmetic damage to the printed product. Therefore, the presence of residual hydrophilic channels is a key bottleneck hindering the improvement of the corrosion resistance of water-based inks.

[0008] Existing technologies typically address the poor corrosion resistance of water-based inks by increasing the crosslinking density of the resin and adding more hydrophobic substances. However, these methods often have significant drawbacks: excessive crosslinking can increase ink brittleness and reduce flexibility, affecting printability and the mechanical properties of the final product; excessively increasing hydrophobicity can also degrade the dispersion stability of the water-based binder, leading to poor storage stability or flocculation during printing.

[0009] Therefore, there is an urgent need to develop a new type of corrosion-resistant and environmentally friendly water-based ink and its preparation method, which can fundamentally solve or significantly reduce the problem of residual hydrophilic channels during the drying and film-forming process while maintaining the inherent environmental advantages of water-based inks and the good dispersibility and film-forming properties of water-based acrylic binders, thereby greatly improving the density and corrosion resistance of the ink coating and broadening the application range of water-based inks in harsh environments. Summary of the Invention

[0010] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a corrosion-resistant and environmentally friendly ink and a preparation method thereof.

[0011] The purpose of the present invention can be achieved through the following technical solutions:

[0012] A corrosion-resistant and environmentally friendly ink comprises the following components: 8-12 wt% of a water-based pigment, 1.7-2.2 wt% of a coloring auxiliary, 0.3-0.4 wt% of a defoamer, 0.25-0.3 wt% of a leveling agent, 0.1-0.12 wt% of a light stabilizer, 1.2-1.5 wt% of a thickener, and the balance being a modified acrylic ester emulsion.

[0013] The modified acrylate emulsion is prepared by the following method:

[0014] Step A1: N,N-dimethylpropanolamine, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry nitrogen was introduced into the mixture. The temperature was controlled at 0-10°C in an ice-water bath. Acryloyl chloride was slowly added and stirred for 1.5-2 hours. The mixture was returned to room temperature and the reaction was continued for 4-5 hours. After the reaction was completed, the mixture was filtered and the tetrahydrofuran was removed by rotary evaporation to obtain an intermediate.

[0015] Furthermore, the amount ratio of N,N-dimethylpropanolamine, acryloyl chloride, triethylamine and anhydrous tetrahydrofuran is 0.1 mol: 0.105-0.11 mol: 15-20 mL: 100-130 mL, and N,N-dimethylpropanolamine and acryloyl chloride are subjected to esterification reaction. The specific reaction route is as follows:

[0016]

[0017] Step A2: The intermediate, 1-bromo-4,4,4-trifluorobutane and toluene are mixed, nitrogen is introduced, potassium carbonate is added, and the temperature is raised to 80-100°C and refluxed for reaction for 10-15 hours. After the reaction is completed, the mixture is filtered and the toluene is removed by vacuum rotary evaporation to obtain a modified monomer;

[0018] Furthermore, the intermediate, 1-bromo-4,4,4-trifluorobutane, potassium carbonate and toluene are used in a ratio of 0.1 mol: 0.15-0.18 mol: 4.5-6 g: 350-400 mL, and the intermediate and 1-bromo-4,4,4-trifluorobutane are subjected to a quaternization reaction. The specific reaction route is as follows:

[0019]

[0020] Step A3: premix butyl acrylate, methyl methacrylate, a modified monomer, and hydroxyethyl acrylate, dissolve ammonium persulfate in deionized water, and disperse the mixture with stirring. Heat to 70-80° C. and stir for 4.5-5.5 hours. After the reaction is complete, adjust the pH to 8 with aqueous ammonia, and then adjust the solid content to 25-28% to obtain a modified acrylate emulsion.

[0021] Furthermore, the usage ratio of butyl acrylate, methyl methacrylate, modified monomer, hydroxyethyl acrylate, ammonium persulfate and deionized water is 1 mol: 0.4-0.5 mol: 0.3-0.42 mol: 0.1-0.15 mol: 0.55-0.7 g: 1.2-1.5 L, and each monomer is addition-polymerized under the initiation of ammonium persulfate to form a polymer resin dispersion.

[0022] Preferably, the coloring auxiliary agent is submicron rutile titanium dioxide, which maintains good dispersion stability in water-based ink, provides strong reflectivity, and makes the pigment color more saturated.

[0023] Preferably, the thickener is a non-ionic waterborne polyurethane formulation that matches the modified acrylate emulsion film-forming substrate.

[0024] Preferably, the defoamer and the leveling agent are both water-based organosilicon preparations, which have significant effects in water-based acrylate dispersion systems and have good corrosion resistance.

[0025] A method for preparing a corrosion-resistant and environmentally friendly ink comprises the following steps: shearing and dispersing a water-based pigment, a coloring auxiliary agent, and a modified acrylic ester emulsion, adding a defoaming agent, a leveling agent, and a light stabilizer, and mixing the mixture; vacuum degassing the mixture, and then adding a thickener and mixing the mixture to obtain the corrosion-resistant and environmentally friendly ink.

[0026] Beneficial effects of the present invention:

[0027] The invention discloses a water-based acrylate emulsion as an ink binder. The emulsion is prepared by esterifying N,N-dimethylpropanolamine and acryloyl chloride to prepare an intermediate, then undergoing a quaternization reaction between 1-bromo-4,4,4-trifluorobutane and the intermediate to prepare a modified monomer, and finally polymerizing the modified monomer, a small amount of hydroxyethyl acrylate and other acrylate monomers in an aqueous phase. Compared with the existing technology, the modified monomer introduces a strongly hydrophilic quaternary ammonium structure into the acrylate polymer chain, reducing the use of existing hydrophilic groups such as hydroxyl and carboxyl. In the aqueous system, the fluorine structure connected by the alkyl group on the side chain has strong hydrophobicity and is then embedded in the interior of the droplet. The exposed quaternary ammonium structure has strong hydrophilicity, which promotes the formation of a water-in-oil dispersed phase. The droplets at the interface containing the quaternary ammonium structure have better dispersibility and stability under the action of like-charge repulsion. During the drying process of the ink, water precipitates from the hydrophilic quaternary ammonium interface, and the fluorine structure with low surface energy migrates to the emulsion spreading interface with high surface energy. On the one hand, the hydrophobic fluorine structure migrates to the bonding interface to close the hydrophilic channel. On the other hand, the electrostatic repulsion between the interfaces is weakened, so that the binder spreads to form a dense ink layer, thereby effectively solving the problem of insufficient corrosion resistance of existing water-based inks due to residual hydrophilic channels. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0029] Example 1, preparation of corrosion-resistant environmentally friendly ink, the specific implementation process is as follows:

[0030] (1) Preparation of modified acrylic emulsion

[0031] Step A1: N,N-dimethylpropanolamine, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry nitrogen was introduced for protection. The temperature was controlled at 10°C in an ice-water bath. Acryloyl chloride was slowly added and stirred for 1.5 hours. The mixture was returned to room temperature and the reaction was continued for 4 hours. The dosage ratio of N,N-dimethylpropanolamine, acryloyl chloride, triethylamine, and anhydrous tetrahydrofuran was 0.1 mol: 0.11 mol: 20 mL: 130 mL. After the reaction, the mixture was filtered and the tetrahydrofuran was removed by rotary evaporation to obtain an intermediate.

[0032] Step A2: The intermediate, 1-bromo-4,4,4-trifluorobutane and toluene were mixed, nitrogen was introduced, potassium carbonate was added and the temperature was raised to 100°C for reflux reaction for 10 hours, wherein the amount ratio of the intermediate, 1-bromo-4,4,4-trifluorobutane, potassium carbonate and toluene was 0.1 mol: 0.18 mol: 6 g: 400 mL. After the reaction was completed, the mixture was filtered and the toluene was removed by vacuum rotary evaporation to obtain a modified monomer.

[0033] Step A3: Premix butyl acrylate, methyl methacrylate, modified monomer, and hydroxyethyl acrylate, dissolve ammonium persulfate in deionized water, add the premix and disperse with high-speed stirring, raise the temperature to 80°C, and stir to react for 4.5 hours. The amount ratio of butyl acrylate, methyl methacrylate, modified monomer, hydroxyethyl acrylate, ammonium persulfate, and deionized water is 1 mol: 0.5 mol: 0.3 mol: 0.15 mol: 0.7 g: 1.5 L. After the reaction, adjust the pH to 8 with aqueous ammonia, and then adjust the solid content to 28% to obtain a modified acrylate emulsion.

[0034] (2) Preparation of ink

[0035] The raw materials are taken according to weight percentage: 12wt% of water-based pigment, and a commercially available TCR405 water-based color paste is used during the implementation process; 2.2wt% of coloring additive, and a commercially available TR50 rutile titanium dioxide with an average particle size of 0.24μm is used during the implementation process; 0.4wt% of defoaming agent, and a SAG-638 silicone preparation is used during the implementation process; 0.25wt% of leveling agent, and a BYK-333 silicone preparation is used during the implementation process; 0.1wt% of light stabilizer, and a commercially available Tinuvin 400-DW raw material is used during the implementation process; 1.2wt% of thickener, and an XS73 non-ionic water-based polyurethane preparation is used during the implementation process; the remainder is a modified acrylate emulsion, which is homemade in this embodiment.

[0036] The water-based pigment, coloring auxiliary agent and modified acrylic ester emulsion are mixed and fed and sheared and dispersed at 1200 rpm, and then a defoamer, a leveling agent and a light stabilizer are added and stirred and mixed. The mixture is vacuum degassed, and finally a thickener is added and stirred at a low speed to obtain a corrosion-resistant and environmentally friendly ink.

[0037] Example 2, preparation of corrosion-resistant environmentally friendly ink, the specific implementation process is as follows:

[0038] (1) Preparation of modified acrylic emulsion

[0039] Step A1: N,N-dimethylpropanolamine, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry nitrogen was introduced for protection. The temperature was controlled at 0°C in an ice-water bath. Acryloyl chloride was slowly added and stirred for 2 hours. The mixture was returned to room temperature and the reaction was continued for 5 hours. The amount ratio of N,N-dimethylpropanolamine, acryloyl chloride, triethylamine, and anhydrous tetrahydrofuran was 0.1 mol: 0.105 mol: 15 mL: 100 mL. After the reaction was completed, the mixture was filtered and the tetrahydrofuran was removed by rotary evaporation to obtain an intermediate.

[0040] Step A2: The intermediate, 1-bromo-4,4,4-trifluorobutane and toluene were mixed, nitrogen was introduced, potassium carbonate was added and the temperature was raised to 80°C and refluxed for 15 hours, wherein the amount ratio of the intermediate, 1-bromo-4,4,4-trifluorobutane, potassium carbonate and toluene was 0.1 mol: 0.15 mol: 4.5 g: 350 mL. After the reaction was completed, the mixture was filtered and the toluene was removed by vacuum rotary evaporation to obtain a modified monomer.

[0041] Step A3: Premix butyl acrylate, methyl methacrylate, modified monomer, and hydroxyethyl acrylate, dissolve ammonium persulfate in deionized water, add the premix and disperse with high-speed stirring, raise the temperature to 70°C, and stir to react for 5.5 hours. The amount ratio of butyl acrylate, methyl methacrylate, modified monomer, hydroxyethyl acrylate, ammonium persulfate, and deionized water is 1 mol: 0.4 mol: 0.42 mol: 0.1 mol: 0.55 g: 1.2 L. After the reaction, adjust the pH to 8 with aqueous ammonia, and then adjust the solid content to 25% to obtain a modified acrylate emulsion.

[0042] (2) Preparation of ink

[0043] The raw materials are taken according to weight percentage: 8wt% water-based pigment, and the commercially available TCR405 water-based color paste is used during the implementation process; 1.7wt% coloring auxiliary agent, and the commercially available TR50 rutile titanium dioxide is used during the implementation process, with an average particle size of 0.24μm; 0.35wt% defoamer, and the SAG-638 silicone preparation is used during the implementation process; 0.3wt% leveling agent, and the BYK-333 silicone preparation is used during the implementation process; 0.12wt% light stabilizer, and the commercially available Tinuvin 400-DW raw material is used during the implementation process; 1.5wt% thickener, and the XS73 non-ionic water-based polyurethane preparation is used during the implementation process; the remainder is modified acrylate emulsion, which is homemade in this embodiment.

[0044] The water-based pigment, coloring auxiliary agent and modified acrylic ester emulsion are mixed and fed and sheared and dispersed at 1200 rpm, and then a defoamer, a leveling agent and a light stabilizer are added and stirred and mixed. The mixture is vacuum degassed, and finally a thickener is added and stirred at a low speed to obtain a corrosion-resistant and environmentally friendly ink.

[0045] Example 3, preparation of corrosion-resistant environmentally friendly ink, the specific implementation process is as follows:

[0046] (1) Preparation of modified acrylic emulsion

[0047] Step A1: N,N-dimethylpropanolamine, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry nitrogen was introduced for protection. The temperature was controlled at 5°C in an ice-water bath. Acryloyl chloride was slowly added and stirred for 1.8 hours. The mixture was returned to room temperature and the reaction was continued for 4.5 hours. The amount ratio of N,N-dimethylpropanolamine, acryloyl chloride, triethylamine, and anhydrous tetrahydrofuran was 0.1 mol:0.108 mol:19 mL:120 mL. After the reaction, the mixture was filtered and the tetrahydrofuran was removed by rotary evaporation to obtain an intermediate.

[0048] Step A2: The intermediate, 1-bromo-4,4,4-trifluorobutane and toluene were mixed, nitrogen was introduced, potassium carbonate was added and the temperature was raised to 90°C and refluxed for 12 hours, wherein the amount ratio of the intermediate, 1-bromo-4,4,4-trifluorobutane, potassium carbonate and toluene was 0.1 mol: 0.17 mol: 5.5 g: 370 mL. After the reaction was completed, the mixture was filtered and the toluene was removed by vacuum rotary evaporation to obtain a modified monomer.

[0049] Step A3: Premix butyl acrylate, methyl methacrylate, modified monomer, and hydroxyethyl acrylate, dissolve ammonium persulfate in deionized water, add the premix and disperse with high-speed stirring, raise the temperature to 75°C, and stir to react for 5 hours. The ratio of butyl acrylate, methyl methacrylate, modified monomer, hydroxyethyl acrylate, ammonium persulfate, and deionized water is 1 mol: 0.45 mol: 0.38 mol: 0.12 mol: 0.65 g: 1.3 L. After the reaction, adjust the pH to 8 with aqueous ammonia, and then adjust the solid content to 26% to obtain a modified acrylate emulsion.

[0050] (2) Preparation of ink

[0051] The raw materials are taken according to weight percentage: 11wt% of water-based pigment, and the commercially available TCR405 water-based color paste is used during the implementation process; 2.1wt% of coloring additive, and the commercially available TR50 rutile titanium dioxide is used during the implementation process, with an average particle size of 0.24μm; 0.3wt% of defoaming agent, and the SAG-638 type silicone preparation is used during the implementation process; 0.25wt% of leveling agent, and the BYK-333 type silicone preparation is used during the implementation process; 0.1wt% of light stabilizer, and the commercially available raw material of Tinuvin 400-DW is used during the implementation process; 1.3wt% of thickener, and the XS73 type non-ionic water-based polyurethane preparation is used during the implementation process; the remainder is modified acrylate emulsion, which is homemade in this embodiment.

[0052] The water-based pigment, coloring auxiliary agent and modified acrylic ester emulsion are mixed and fed and sheared and dispersed at 1200 rpm, and then a defoamer, a leveling agent and a light stabilizer are added and stirred and mixed. The mixture is vacuum degassed, and finally a thickener is added and stirred at a low speed to obtain a corrosion-resistant and environmentally friendly ink.

[0053] Example 4, preparation of corrosion-resistant environmentally friendly ink, the specific implementation process is as follows:

[0054] (1) Preparation of modified acrylic emulsion

[0055] Step A1: N,N-dimethylpropanolamine, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry nitrogen was introduced for protection. The temperature was controlled at 5°C in an ice-water bath. Acryloyl chloride was slowly added and stirred for 2 hours. The mixture was returned to room temperature and the reaction was continued for 4 hours. The dosage ratio of N,N-dimethylpropanolamine, acryloyl chloride, triethylamine, and anhydrous tetrahydrofuran was 0.1 mol: 0.107 mol: 20 mL: 120 mL. After the reaction, the mixture was filtered and the tetrahydrofuran was removed by rotary evaporation to obtain an intermediate.

[0056] Step A2: The intermediate, 1-bromo-4,4,4-trifluorobutane and toluene were mixed, nitrogen was introduced, potassium carbonate was added and the temperature was raised to 85°C and refluxed for 14 hours, wherein the amount ratio of the intermediate, 1-bromo-4,4,4-trifluorobutane, potassium carbonate and toluene was 0.1 mol: 0.15 mol: 5 g: 380 mL. After the reaction was completed, the mixture was filtered and the toluene was removed by vacuum rotary evaporation to obtain a modified monomer.

[0057] Step A3: Premix butyl acrylate, methyl methacrylate, modified monomer, and hydroxyethyl acrylate, dissolve ammonium persulfate in deionized water, add the premix, and disperse with high-speed stirring. Raise the temperature to 75° C. and stir to react for 5.2 hours. The ratio of butyl acrylate, methyl methacrylate, modified monomer, hydroxyethyl acrylate, ammonium persulfate, and deionized water is 1 mol: 0.42 mol: 0.4 mol: 0.15 mol: 0.65 g: 1.4 L. After the reaction, adjust the pH to 8 with aqueous ammonia, and then adjust the solid content to 25-28% to obtain a modified acrylate emulsion.

[0058] (2) Preparation of ink

[0059] The raw materials are taken according to weight percentage: 9wt% water-based pigment, and the commercially available TCR405 water-based color paste is used during the implementation process; 1.8wt% coloring additive, and the commercially available TR50 rutile titanium dioxide is used during the implementation process, with an average particle size of 0.24μm; 0.35wt% defoamer, and the SAG-638 silicone preparation is used during the implementation process; 0.28wt% leveling agent, and the BYK-333 silicone preparation is used during the implementation process; 0.11wt% light stabilizer, and the commercially available Tinuvin 400-DW raw material is used during the implementation process; 1.4wt% thickener, and the XS73 non-ionic water-based polyurethane preparation is used during the implementation process; the remainder is modified acrylate emulsion, which is homemade in this embodiment.

[0060] The water-based pigment, coloring auxiliary agent and modified acrylic ester emulsion are mixed and fed and sheared and dispersed at 1200 rpm, and then a defoamer, a leveling agent and a light stabilizer are added and stirred and mixed. The mixture is vacuum degassed, and finally a thickener is added and stirred at a low speed to obtain a corrosion-resistant and environmentally friendly ink.

[0061] In Comparative Example 1, commercially available SEACRYL 11K38 water-based acrylic resin was selected and adjusted to a solid content of 27% with deionized water. An equivalent amount of alternative acrylic emulsion was used as in Example 4, and the remaining steps were exactly the same.

[0062] Comparative Example 2, referring to the existing composite technology system, adopts quaternary ammonium salt and fluoride blending to modify the ink, specifically referring to Comparative Example 1, 0.8wt% of dodecyltrimethylammonium chloride and 4.5wt% of PFA 6910GZ type fluoroplastic dispersion are compounded into the diluted aqueous acrylic resin, and the rest of the implementation is exactly the same.

[0063] Samples were taken from the ink prepared as described above and tested for anti-settling stability according to ASTM D869-2021. The ink was printed on a glass slide and then dried and cured. The ink was then tested for acid resistance (5% H2SO4, 240 hours), alkali resistance (3% NaOH, 240 hours), and salt resistance (5% NaCl, 500 hours) according to GB / T 1763-1979. The water absorption rate was tested according to ASTM D4942-20. The specific test results are shown in Table 1:

[0064] Table 1 Test results of ink layer's resistance to media corrosion

[0065] Acid resistance performance Alkali resistance performance Salt resistance performance Example 1 Slight haze, whitening Slight haze No visible change Example 2 Slight haze No visible change No visible change Example 3 Slight haze Slight haze No visible change Example 4 Slight haze No visible change No visible change Comparative Example 1 Obvious color difference, severe whitening Obvious color difference, severe haze Obvious haze, whitening Comparative Example 2 Visible whitening spots Visible whitening spots Slight haze

[0066] In the acid, alkali and salt resistance tests, the ink layer of Example 1 showed no obvious corrosion phenomenon in its colored state, and had better corrosion resistance than the comparative example. Among them, Comparative Example 2 also showed certain corrosion resistance, but visible color spots appeared on the surface of the ink layer. Analysis showed that this may be because the compatibility of fluoride in the ink was poor, and it migrated to the surface of the ink layer during the ink curing process, playing a certain shielding and corrosion resistance role. The uneven migration of fluoride caused surface corrosion spots.

[0067] Table 2 Test results of ink stability and ink layer water absorption

[0068] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Instability index 0.20 0.13 0.18 0.15 0.29 0.65 Water absorption rate / % 3.63 2.55 3.41 2.92 8.14 5.39

[0069] It can be seen from the test data in Table 2 that the ink of Example 1 has high stability, is conducive to the uniformity of ink film formation, and has an extremely low water absorption rate of the ink layer, which prevents erosion by corrosive media.

[0070] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0071] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A corrosion-resistant and environmentally friendly ink, characterized in that: The specific components are: 8-12wt% of water-based pigment, 1.7-2.2wt% of coloring auxiliary agent, 0.3-0.4wt% of defoaming agent, 0.25-0.3wt% of leveling agent, 0.1-0.12wt% of light stabilizer and 1.2-1.5wt% of thickener, and the balance is modified acrylic emulsion; The modified acrylate emulsion is prepared by the following method: Step A1: N,N-dimethylpropanolamine, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry nitrogen was introduced into the mixture. The temperature was controlled at 0-10°C in an ice-water bath. Acryloyl chloride was slowly added and stirred for 1.5-2 hours. The mixture was returned to room temperature and the reaction was continued for 4-5 hours to prepare an intermediate. Step A2: The intermediate, 1-bromo-4,4,4-trifluorobutane and toluene are mixed, nitrogen is introduced, potassium carbonate is added, and the mixture is heated to 80-100° C. and refluxed for 10-15 hours to prepare a modified monomer; Step A3: Premix butyl acrylate, methyl methacrylate, a modified monomer, and hydroxyethyl acrylate. Dissolve ammonium persulfate in deionized water and disperse the mixture with stirring. Heat to 70-80°C and stir to react for 4.5-5.5 hours. After the reaction is complete, adjust the pH to 8 with aqueous ammonia, and then adjust the solid content to 25-28% to obtain a modified acrylate emulsion.

2. The corrosion-resistant and environmentally friendly ink according to claim 1, characterized in that: The usage ratio of N,N-dimethylpropanolamine, acryloyl chloride, triethylamine and anhydrous tetrahydrofuran is 0.1 mol: 0.105-0.11 mol: 15-20 mL: 100-130 mL.

3. The corrosion-resistant and environmentally friendly ink according to claim 2, characterized in that: The usage ratio of the intermediate, 1-bromo-4,4,4-trifluorobutane, potassium carbonate and toluene is 0.1 mol: 0.15-0.18 mol: 4.5-6 g: 350-400 mL.

4. The corrosion-resistant and environmentally friendly ink according to claim 3, characterized in that: The usage ratio of butyl acrylate, methyl methacrylate, modified monomer, hydroxyethyl acrylate, ammonium persulfate and deionized water is 1 mol: 0.4-0.5 mol: 0.3-0.42 mol: 0.1-0.15 mol: 0.55-0.7 g: 1.2-1.5 L.

5. The corrosion-resistant and environmentally friendly ink according to claim 1, characterized in that: The coloring auxiliary agent is submicron rutile titanium dioxide.

6. The corrosion-resistant and environmentally friendly ink according to claim 1, characterized in that: The thickener is a non-ionic water-based polyurethane preparation.

7. The corrosion-resistant and environmentally friendly ink according to claim 1, characterized in that: Defoamers and leveling agents are both water-based silicone preparations.

8. A method for preparing the corrosion-resistant and environmentally friendly ink according to any one of claims 1 to 7, characterized in that: Specifically, the water-based pigment, coloring additive and modified acrylic emulsion are sheared and dispersed, a defoaming agent, a leveling agent and a light stabilizer are added and mixed, and after vacuum degassing, a thickener is added and mixed to obtain a corrosion-resistant and environmentally friendly ink.